WO2005058260A1 - Caring oxidation colouring agent in tube - Google Patents

Caring oxidation colouring agent in tube Download PDF

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Publication number
WO2005058260A1
WO2005058260A1 PCT/EP2004/013932 EP2004013932W WO2005058260A1 WO 2005058260 A1 WO2005058260 A1 WO 2005058260A1 EP 2004013932 W EP2004013932 W EP 2004013932W WO 2005058260 A1 WO2005058260 A1 WO 2005058260A1
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Prior art keywords
acid
preparation
agent according
amino
derivatives
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PCT/EP2004/013932
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German (de)
French (fr)
Inventor
Astrid Kleen
Mustafa Akram
Stefan Hoepfner
Hartmut Manneck
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to EP04803611A priority Critical patent/EP1699425A1/en
Publication of WO2005058260A1 publication Critical patent/WO2005058260A1/en
Priority to US11/471,101 priority patent/US7294153B2/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/416—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67—Vitamins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9706—Algae
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9755—Gymnosperms [Coniferophyta]
    • A61K8/9761—Cupressaceae [Cypress family], e.g. juniper or cypress
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9755—Gymnosperms [Coniferophyta]
    • A61K8/9767—Pinaceae [Pine family], e.g. pine or cedar
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9789—Magnoliopsida [dicotyledons]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9783—Angiosperms [Magnoliophyta]
    • A61K8/9794—Liliopsida [monocotyledons]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits

Definitions

  • the present invention relates to a two-component agent for coloring keratin fibers, which is assembled in a two-chamber tube, a corresponding two-chamber tube and a method for dyeing keratin fibers using these agents.
  • Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much undesired shift in nuances or even a visible "discoloration" occurs much more quickly.
  • oxidation dyes are used for permanent, intensive dyeings with appropriate fastness properties.
  • Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components.
  • the developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components.
  • the oxidation coloring agents are characterized by excellent, long-lasting coloring results.
  • a mixture of a larger number of oxidation dye precursors usually has to be used for natural-looking dyeings; in many cases direct dyes are still used for shading.
  • care products influence the natural structure and properties of the hair.
  • a care product for example, the wet and dry combability of the hair, the hold, the strength and the fullness of the hair can be optimized or the hair can be protected from increased split ends.
  • the hair is treated with special active ingredients, for example quaternary ammonium salts or special polymers.
  • special active ingredients for example quaternary ammonium salts or special polymers.
  • this treatment improves the combability, hold and fullness of the hair and reduces the split rate.
  • the active ingredients available generally act preferentially on the hair surface. Active ingredients are known which give hair shine, hold, fullness, better wet or dry combability or prevent split ends. However, just as important as the external appearance of the hair is the internal structural cohesion of the hair fibers, which can be greatly influenced in particular in oxidative and reductive processes such as coloring and perms. Active substances that can counteract this change in the internal structure of the fibers in the long term have also been proposed.
  • combination preparations have been developed in order to reduce the effort of the usual multi-stage processes, particularly when used directly by consumers.
  • these preparations also contain active ingredients which were formerly reserved for the hair aftertreatment agents. The consumer thus saves one application step; At the same time, the packaging effort is reduced because one product is used less.
  • the present invention therefore firstly relates to two-component agents for dyeing keratin fibers, comprising a first preparation (A) containing at least one oxidation dye precursor and a second preparation (B) containing at least one care substance, the two preparations being separate from one another in the chambers Two-chamber tubes are made up.
  • the two-component agents according to the invention are notable for excellent care and coloring performance and high stability. It also ensures that the consumer applies the components in the mixing ratio planned by the manufacturer. In this way, on the one hand, product safety is increased and, on the other hand, it is guaranteed that the product achieves the desired performance.
  • preparation (A) contains at least one developer component.
  • Primary aromatic amines with a further free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and their derivatives are usually used as developer components ,
  • P-Phenylenediamine derivatives of the formula (E1) are particularly preferred
  • G 1 represents a hydrogen atom, a C to C 4 alkyl radical, a C to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a (C to C) alkoxy- (d- to C) - alkyl radical, a 4'-aminophenyl radical or a C to C 4 alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical; G 2 represents a hydrogen atom, a C to C alkyl radical, a C to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a (C to C 4 ) alkoxy (C to C) alkyl radical or a C to C 4 alkyl radical which is substituted by a nitrogen-containing group; G 3 represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom,
  • Examples of the Cr to C alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Cr to C 4 alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C to C -hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C 2 - to C 4 -polyhydroxyalkyl group is the 1, 2-dihydroxyethyl.
  • halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here.
  • nitrogen-containing groups of the formula (E1) are in particular the amino groups, Cr to C 4 -monoalkylamino groups, d- to C 4 -dialkylamino groups, C to C 4 -trialkylammonium groups, C to C-monohydroxyalkylamino groups, imidazolinium and ammonium.
  • Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine , 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (ß-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (ß-hydroxyethyl) amino -2-methylaniline, 4- N, N
  • p-phenylenediamine derivatives of the formula (E1) which are particularly preferred are p-phenylenediamine, p-toluenediamine, 2- ( ⁇ -hydroxyethyl) -p-phenylenediamine, 2- ( ⁇ , ⁇ -dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.
  • developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
  • binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:
  • Z 1 and Z 2 independently of one another represent a hydroxyl or NH 2 radical which is optionally substituted by a C to C 4 alkyl radical, by a C to C 4 hydroxyalkyl radical and / or by a bridging Y or which is optionally Is part of a bridging ring system, -
  • the bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is interrupted by one or more nitrogen-containing groups and / or one or more hetero atoms such as oxygen, sulfur or nitrogen atoms or may be terminated and may be substituted by one or more hydroxyl or d to C 8 alkoxy radicals, or a direct bond,
  • G 5 and G 6 are each independently a hydrogen or halogen atom, a d- to C 4 alkyl, a d- to C monohydroxyalkyl radical, a C 2 - to C 4 - polyhydroxyalkyl radical, a C to C 4 -aminoalkyl or a direct connection to bridge Y,
  • G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently of one another represent a hydrogen atom, a direct bond to the bridging Y or a d- to C -alkyl radical, with the provisos that
  • the compounds of formula (E2) contain only one bridge Y per molecule and the compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.
  • Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis- ( ⁇ -hydroxyethyl) -N, N , -bis- (4'-aminophenyl) -1, 3-diamino-propan-2-ol, N, N'-bis ( ⁇ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis - (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) -tetramethylene-diamine, N, N'-bis- (4-methyl-aminophenyl) -tetramethylene-diamine, N, N'-diethyl-N, N , -bis- (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-
  • dinuclear developer components of the formula (E2) are N, N'-bis (ß-hydroxyethyl) -N, N , -bis- (4'-aminophenyl) -1, 3-diamino-propan-2-ol, bis - (2-Hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4'-aminophenyl) -1 , 4-diazacycloheptane and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of their physiologically tolerable salts.
  • Bis- (2-hydroxy-5-aminophenyl) methane is a very particularly preferred dinuclear developer component of the formula (E2).
  • P-Aminophenol derivatives of the formula (E3) are particularly preferred
  • - G 13 represents a hydrogen atom, a halogen atom, ad- to C 4 -alkyl residue, ad- to C 4 -monohydroxyalkyl residue, a C 2 - to C 4 -polyhydroxyalkyl residue, a (Cr to C 4 ) - alkoxy- ( d- to C 4 ) -alkyl radical, a d- to C -aminoalkyl radical, a hydroxy- (C to C 4 ) -alkylamino radical, a Cr to C 4 -hydroxyalkoxy radical, ad- to C 4 -hydroxyalkyl- (d-bis C 4 ) aminoalkyl or a (di-C r to C 4 alkylamino) - (C to C 4 ) alkyl, and
  • - G 14 represents a hydrogen or halogen atom, a Cr to C alkyl group, a d to C 4 monohydroxyalkyl group, a C 2 to C 4 polyhydroxyalkyl group, a (d to C 4 ) alkoxy (i.e. - to C 4 ) -alkyl radical, a C r to C 4 -aminoalkyl radical or a C to C 4 -cyanoalkyl radical,
  • - G 15 represents hydrogen, a C r to C alkyl radical, a C to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
  • - G 16 represents hydrogen or a halogen atom.
  • Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2- Hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (ß-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2- methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2- ( ⁇ , ß-dihydroxyethyl) phenol, 4-amino-2- fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically tolerable salts.
  • Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( ⁇ , ⁇ -dihydroxyethyl) phenol and 4-amino- 2- (diethylaminomethyl) -phenol.
  • the developer component can be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
  • the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.
  • heterocyclic developer components such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.
  • Preferred pyridine derivatives are, in particular, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine , 2,3-diamino-6-methoxy-pyridine, 2- (ß-
  • MethoxyethyI amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.
  • Preferred pyrimidine derivatives are, in particular, the compounds which are described in German patent DE 2 359 399, Japanese laid-open patent publication JP 02019576 A2 or in laid-open publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- triaminopyrimidine.
  • Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4.5 -Diamino-1-methylpyrazole, 4,5- diamino-1 - (ß-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 - (4'-chlorobenzyl) - pyrazole, 4,5- Diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5- Diamino-1-methyl-3-phenylpyrazole, 4-amino-1, 3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-buty
  • Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of pyrazole- [1,5-a] -pyrimidine of the following formula (E4) and its tautomeric forms, provided there is a tautomeric equilibrium:
  • G 17 , G 18 , G 19 and G 20 independently represent a hydrogen atom, a Cr to C 4 alkyl radical, an aryl radical, a C to C hydroxyalkyl radical, a C 2 to C polyhydroxyalkyl radical a (C to C 4 ) -alkoxy- (Cr to C 4 ) -alkyl, a C to C 4 -aminoalkyl radical, which can optionally be protected by an acetyl-ureide or a sulfonyl radical, a (C to C) -alkylamino- (d- to C) -alkyl radical, a di - [(d- to C 4 ) -alkyl] - (Cr to C 4 ) -aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links , ad- to C 4 -hydroxyalkyl or di- (d- to C 4 )
  • the X radicals independently of one another represent a hydrogen atom, a C to C 4 alkyl radical, an aryl radical, a d to C 4 hydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a C to C 4 Aminoalkyl radical, a (C to C 4 ) alkylamino (d to C 4 ) alkyl radical, a di - [(C to C) alkyl] - (d to C) aminoalkyl radical, the dialkyl radicals optionally having one Form carbon cycle or a heterocycle with 5 or 6 chain links, a C to C 4 hydroxyalkyl or a di (C to C 4 hydroxyalkyl) aminoalkyl radical, an amino radical, a d to C 4 alkyl or di - (d- to C 4 -hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1,
  • pyrazole- [1, 5-a] pyrimidines of the above formula (E4) one can mention in particular: pyrazole- [1, 5-a] pyrimidine-3,7-diamine; 2,5-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine; Pyrazole- [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethylpyrazole- [1,5-a] pyrimidine-3,5-diamine; 3-aminopyrazole- [1,5-a] pyrimidin-7-ol; 3-aminopyrazole- [1,5-a] pyrimidin-5-ol; 2- (3-aminopyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol; 2- (7-aminopyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-aminopyrazole- [1,5]
  • the pyrazole [1, 5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.
  • preparation (A) contains at least one coupler component.
  • M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components.
  • Suitable coupler substances are in particular 1-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxy-naphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1 -Phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol , 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresor
  • Coupler components preferred according to the invention are m-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2, 6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methyiphenol, 5- (2'- Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4 -Dichlor-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example
  • Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
  • Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2 -Methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2.7 - Dihydroxynaphthalene and 2,3-
  • Coupler components which are particularly preferred according to the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
  • the preparation (A) has at least one developer component selected from p-phenylenediamine, p-toluenediamine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p -phenylenediamine, 1- (2-hydroxyethyl) -2,5-diaminobenzene, 3-methyl-4-aminophenol, bis- (2-hydroxy-5-amino- phenyl) methane, 2,4,5, 6-tetraaminopyrimidine and 1- (2-hydroxyethyl) -4,5-diaminopyrazole, and / or at least one further coupler component selected from 2- (2,4-diaminophenoxy) ethanol , 1,3-bis- (2,4-diaminophenoxy) propane, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 2-methylresorcinol, 4-chlor
  • the developer components and the coupler components are preferably present in preparation (A) in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, in each case based on the total two-component agent.
  • Developer components and coupler components are generally used in approximately molar amounts to one another. If molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can be included.
  • Preparation (A) according to the invention can furthermore contain a precursor of a nature-analogous dye.
  • Those indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes.
  • These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group.
  • the colorants contain at least one indole and / or indoline derivative.
  • R 1 represents hydrogen, a dC 4 -alkyl group or a dC 4 -hydroxy-alkyl group
  • R 2 stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation
  • R 3 represents hydrogen or a dC -alkyl group
  • - R 4 stands for hydrogen, a dC -alkyl group or a group -CO-R 6 , in which R 6 stands for a CrC -alkyl group
  • R 6 stands for a CrC -alkyl group
  • R 5 stands for one of the groups mentioned under R 4 , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.
  • indoline Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline,
  • N-methyl-5,6-dihydroxyindoline N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially the 5 6-Dihydroxyindolin.
  • R 1 stands for hydrogen, a CC 4 -alkyl group or a dC 4 -hydroxyalkyl group
  • R 2 stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation
  • R 3 stands for hydrogen or a dC 4 -alkyl group
  • R 4 stands for hydrogen, a dd-alkyl group or a group -CO-R 6 , in which R 6 stands for a CrC 4 -alkyl group
  • R 5 stands for one of those under R. 4 mentioned groups, as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.
  • Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
  • N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 are to be emphasized -Dihydroxyindol.
  • the indoline and indole derivatives can be in the two-component compositions according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for.
  • B. the hydrochlorides, sulfates and hydrobromides can be used.
  • the indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight, based in each case on the total two-component agent.
  • the indoline or indole derivative in hair colorants in combination with at least one amino acid or an oligopeptide.
  • the amino acid is advantageously an ⁇ -amino acid; very particularly preferred ⁇ -amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
  • the preparation (A) according to the invention can contain one or more substantive dyes for shading.
  • Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.
  • Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds and 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis (ß-hydoxyethyl) -amino-2-nitrobenzene, 3-nitro-4- (ß-hydroxyethyl ) -aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxye
  • preparation (A) contains a cationic direct dye.
  • a cationic direct dye such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14
  • aromatic systems which are substituted by a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
  • a quaternary nitrogen group such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17
  • substantive dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as described, for example, in EP-A2-998 908, to which at this point explicit reference is made to claims 6 to 11.
  • Preferred cationic direct dyes of group (c) are in particular the following compounds:
  • the compounds of the formulas (DZ1), (DZ3) and (DZ5) which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic direct dyes of group (c).
  • the cationic direct dyes which are sold under the trademark Arianor ® are, according to the invention also very particularly preferred cationic direct dyes.
  • the agents according to the invention in this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total two-component agent.
  • preparations according to the invention can also contain naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.
  • naturally occurring dyes such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.
  • the hair colorants according to the invention may also contain minor components in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.
  • the two-component agents according to the invention contain at least one care substance in the preparation (B) as an ingredient essential to the invention.
  • the two-component agent according to the invention contains at least one cationic surfactant as a care substance.
  • Cationic surfactants of the type of the quaternary ammonium compounds, the esterquats and the amidoamines are preferred according to the invention.
  • Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B.
  • cetyltrimethylammonium chloride stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the Veriditchazol known under the INCI names Quaternium-27 and Quaternium-83.
  • the long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
  • Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element.
  • Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines.
  • Such products are sold, for example, under the trademarks Stepantex ® , Dehyquart ® and Armocare ® .
  • the products Armocare ® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ® F-75, Dehyquart ® C-4046, Dehyquart ® L80 and Dehyquart ® AU-35 are examples of such esterquats .
  • the alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
  • An inventively particularly suitable compound from this group of substances that available under the name Tegoamid ® S 18 commercially stearamidopropyldimethylamine is dimethylamine.
  • the cationic surfactants are preferably contained in the two-component compositions according to the invention in amounts of 0.05 to 10% by weight, based on the entire application preparation. Amounts of 0.1 to 5% by weight are particularly preferred.
  • the two-component agents contain at least one caring polymer as a care substance.
  • a first group of caring polymers are the cationic polymers.
  • Cationic polymers are understood according to the invention to mean polymers which have a group in the main and / or side chain which can be “temporary” or “permanent” cationic.
  • polymers which have a cationic group irrespective of the pH of the composition are referred to as "permanently cationic".
  • These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group.
  • Preferred cationic groups are quaternary ammonium groups.
  • those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain composed of acrylic acid, methacrylic acid or their derivatives have proven to be particularly suitable.
  • Suitable physiologically acceptable counterions X " are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions.
  • halide ions in particular chloride, are preferred.
  • a particularly suitable homopolymer is, if desired crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37.
  • the crosslinking can be carried out with the aid of polyolefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ether, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose.
  • Methylene bisacrylamide is a preferred crosslinking agent.
  • the homopolymer is preferably used in the form of a non-aqueous polymer dispersion which should not have a polymer content below 30% by weight.
  • a non-aqueous polymer dispersion which should not have a polymer content below 30% by weight.
  • Such polymer dispersions are available under the names Salcare ® SC 95 (approx. 50% polymer content, further components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1-Trideceth- 6)) and Salcare ® SC 96 (approx.
  • Copolymers with monomer units according to formula (G1-I) preferably contain acrylamide, methacrylamide, C 4 -4 alkyl acrylate and C 1-4 alkyl methacrylate as nonionic monomer units.
  • acrylamide is particularly preferred.
  • these copolymers can also be crosslinked.
  • a preferred copolymer according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer.
  • Celquat ® and Polymer JR ® Quaternized cellulose derivatives, as are commercially available under the names Celquat ® and Polymer JR ® .
  • the compounds Celquat ® H 100, Celquat ® L 200 and Polymer JR ® 400 are preferred quaternized cellulose derivatives,
  • honey for example the commercial product Honeyquat ® 50,
  • cationic guar derivatives such as, in particular, the products sold under the trade names Cosmedia ® Guar and Jaguar ® ,
  • - polysiloxanes containing quaternary groups such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized Trimethylsilylamodi- methicone), Dow Corning ® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone ), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt), diquaternary polydimethylsiloxanes, Quaternium-80),
  • Vinylpyrrolidone-vinylimidazolium methochloride copolymers as are offered under the names Luviquat ® FC 370, FC 550, FC 905 and HM 552,
  • Polyquaternium 2 Polyquaternium 17, Polyquatemium 18 and Polyquaternium 27 polymers with quaternary nitrogen atoms in the main polymer chain.
  • copolymers of vinyl pyrrolidone such as those available as commercial products Copolymer 845 (manufacturer: ISP), Gaffix ® VC 713 (manufacturer: ISP), Gafquat ® ASCP 1011, Gafquat ® HS 110, Luviquat ® 8155 and Luviquat ® MS 370 are.
  • cationic polymers that can be used according to the invention are the so-called “temporarily cationic” polymers. These polymers usually contain an amino group which is present as a quaternary ammonium group at certain pH values and is therefore cationic. Preferably, for example, are chitosan and its derivatives, such as 101 are freely available commercially, for example under the trade names Hydagen CMF ®, Hydagen HCMF ®, Kytamer ® PC and Chitolam ® NB /.
  • cationic polymers employed are cationic cellulose derivatives and chitosan and its derivatives, in particular the commercial products Polymer ® JR 400, Hydagen ® HCMF and Kytamer ® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat ® 50, cationic Alkyl polyglycodides according to DE-PS 44 13 686 and polymers of the type Polyquatemium-37.
  • cationized protein hydrolyzates are to be counted among the cationic polymers, the underlying protein hydrolyzate being derived from animals, for example from collagen, milk or keratin, from plants, for example from wheat, corn, rice, potatoes, soy or almonds, from marine life forms, for example from fish collagen or algae, or biotechnologically obtained protein hydrolyzates.
  • the protein hydrolysates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis.
  • cationic protein hydrolyzates are those whose underlying protein content has a molecular weight of 100 to 25,000 Daltons, preferably 250 to 5000 Daltons.
  • Cationic protein hydrolyzates also include quaternized amino acids and their mixtures. The quaternization of protein hydrolyzates or amino acids becomes common using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides.
  • the cationic protein hydrolyzates can also be further derivatized.
  • inventive cationic protein hydrolysates and derivatives are under the INCI - th names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 Street, NW, Suite 300 , Washington, DC 20036-4702) and commercially available products: Cocodimonium hydroxypropyl hydrolyzed collagen, Cocodimonium hydroxypropyl hydrolyzed casein, Cocodimonium hydroxypropyl hydrolyzed collagen, Cocodimonium hydroxypropyl hydrolyzed hair keratin, Cocodimonium hydroxypropyl hydrolyzed keratin, Cocodimonium hydroxypropyl hydrolyzed Rice Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCI, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein
  • the plant-based cationic protein hydrolyzates and derivatives are very particularly preferred.
  • Further care polymers that can be used according to the invention are the amphoteric compounds mentioned in British Patent Application 2 104 091, European Patent Application 47 714, European Patent Application 217274, European Patent Application 283 817 and German Patent Application 28 17 369.
  • Amphoteric polymers which are preferably used are those polymers which essentially consist of one another
  • these compounds can be used both directly and in salt form, which is obtained by neutralizing the polymers, for example with an alkali metal hydroxide.
  • an alkali metal hydroxide for example, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium carbonate, sodium sulfate, sodium bicarbonate, sodium sulfate, sodium sulfate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium
  • the two-component agents according to the invention preferably contain the caring, cationic polymers in an amount of 0.01 to 5% by weight, in particular in an amount of 0.1 to 2% by weight, based in each case on the entire application preparation.
  • the two-component agents according to the invention contain at least one UV filter.
  • the suitable according to the invention UV filters are not subject to any general restrictions with regard to their structure and physical properties. Rather, all UV filters that can be used in the cosmetics sector are suitable, the absorption maximum of which lies in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC ( ⁇ 280 nm) range. UV filters with an absorption maximum in the UVB range, in particular in the range from approximately 280 to approximately 300 nm, are particularly preferred.
  • the UV filters preferred according to the invention can be selected, for example, from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoien and o-aminobenzoic acid esters.
  • UV filters which can be used according to the invention are 4-amino-benzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline-methyl sulfate, 3,3,5-trimethyl-cyclohexyl-salicylate (homosalates ), 2-Hydroxy-4-methoxy-benzophenone (Benzophenone-3; Uvinul ® M 40, Uvasorb ® MET, Neo Heliopan ® BB, Eusolex ® 4360), 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium - and triethanolamine salts (phenylbenzimidazole sulfonic acid; Parsol ® HS; Neo Heliopan ® Hydro), 3,3 '- (1, 4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxo-bicyclo- [2.2.1] hept-1-yl-methane-sulfonic acid
  • 2-hydroxy-4-methoxy-benzophenone, 2-phenylbenzimidazole-5-sulfonic acid and their potassium, sodium and triethanolamine salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) are very particularly preferred.
  • 2-hydroxy-4-methoxy-benzophenone, 2-phenylbenzimidazole-5-sulfonic acid and their potassium, sodium and triethanolamine salts 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) are very particularly preferred.
  • 2-methoxycinnamic acid 2-ethylhexyl ester 4-methoxycinnamic acid 2-ethyl
  • Preferred UV filters are those whose molar extinction coefficient at the absorption maximum is above 15,000, in particular above 20,000.
  • the water-insoluble compound has, in the context of the teaching according to the invention, the higher activity than those water-soluble compounds which differ from it by one or more additional ionic groups.
  • water-insoluble are those UV filters which do not dissolve in water at 20 ° C. by more than 1% by weight, in particular not more than 0.1% by weight.
  • these compounds should be at least 0.1, in particular at least 1% by weight soluble in conventional cosmetic oil components at room temperature.
  • those UV filters are preferred which have a cationic group, in particular a quaternary ammonium group.
  • UV filters have the general structure U - Q.
  • the structural part U stands for a group that absorbs UV rays.
  • this group can be derived from the known UV filters mentioned above, which can be used in the cosmetics sector, in which a group, usually a hydrogen atom, of the UV filter is replaced by a cationic group Q, in particular with a quaternary amino function ,
  • Structural parts U which are derived from cinnamic acid amide or from N, N-dimethylamino-benzoic acid amide are preferred according to the invention.
  • the structural parts U can in principle be selected so that the absorption maximum of the UV filter can be both in the UVA (315-40O nm) and UVB (280-315 nm) or in the UVC ( ⁇ 280 nm) range.
  • UV filters with an absorption maximum in the UVB range in particular in the range from approximately 280 to approximately 300 nm, are particularly preferred.
  • structural part U is preferably selected such that the molar extinction coefficient of the UV filter at the absorption maximum is above 15,000, in particular above 20,000.
  • the structural part Q preferably contains a quaternary ammonium group as the cationic group.
  • This quaternary ammonium group can in principle directly with the structural part U be connected so that the structural part U represents one of the four substituents of the positively charged nitrogen atom.
  • one of the four substituents on the positively charged nitrogen atom is preferably a group, in particular an alkylene group having 2 to 6 carbon atoms, which functions as a connection between the structural part U and the positively charged nitrogen atom.
  • the group Q has the general structure - (CH 2 ) X -N + R 1 R 2 R 3 X " , in which x represents an integer from 1 to 4, R 1 and R 2 independently of one another represent C 1 -4 - alkyl groups, R 3 stands for a C 1-22 alkyl group or a benzyl group and X " for a physiologically acceptable anion.
  • x preferably stands for the number 3, R 1 and R 2 each for a methyl group and R 3 either for a methyl group or a saturated or unsaturated, linear or branched hydrocarbon chain with 8 to 22, in particular 10 to 18, carbon atoms ,
  • Physiologically compatible anions are, for example, inorganic anions such as halides, in particular chloride, bromide and fluoride, sulfate ions and phosphate ions, and organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.
  • inorganic anions such as halides, in particular chloride, bromide and fluoride, sulfate ions and phosphate ions
  • organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.
  • UV filters with cationic groups are the commercially available compounds cinnamic acid-trimethylammonium chloride (lncroquat ® UV 283) and dodecyl tosylate (Escalol ® HP 610).
  • the teaching according to the invention also includes the use of a combination of several UV filters.
  • the combination of at least one water-insoluble UV filter with at least one UV filter with a cationic group is preferred.
  • the UV filters are usually contained in the agents according to the invention in amounts of 0.01-5% by weight, based on the entire application preparation. Amounts of 0.1-2.5% by weight are preferred.
  • the two-component agents according to the invention contain at least one vitamin, one provitamin, one vitamin precursor and / or one of their derivatives as a care substance.
  • Vitamins, pro-vitamins and vitamin precursors which are usually assigned to groups A, B, C, E, F and H are preferred according to the invention.
  • vitamin A and 3,4-didehydroretinol (vitamin A 2 ) belong to the group of substances called vitamin A.
  • ⁇ -carotene is the provitamin of retinol.
  • vitamin A comes as vitamin A component Acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as palmitate and acetate are considered The preparations used according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight , based on the entire application preparation.
  • the vitamin B group or the vitamin B complex include u. a.
  • Vitamin B 2 (riboflavin)
  • nicotinic acid and nicotinamide are often listed under this name. Eleven preferred according to the invention is the nicotinic acid amide, which is preferably contained in the IV compositions according to the invention in amounts of 0.05 to 1% by weight, based on the entire application preparation.
  • panthenol and / or pantolactone is preferably used.
  • Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and cationically derivatized panthenols. Individual representatives are, for example, panthenol triacetate, panthenol monoethyl ether and its monoacetate and the cationic panthenol derivatives disclosed in WO 92/13829.
  • the compounds of the vitamin B 5 type mentioned are preferably present in the agents according to the invention in amounts of 0.05-10% by weight, based on the entire application preparation. Amounts of 0.1-5% by weight are particularly preferred.
  • Vitamin B 6 (pyridoxine, pyridoxamine and pyridoxal).
  • the compounds of the vitamin B 6 type mentioned are preferably present in the agents according to the invention in amounts of 0.01-5% by weight, based on the entire application preparation. Amounts of 0.05-1% by weight are particularly preferred.
  • Vitamin C (ascorbic acid). Vitamin C is used in the agents used according to the invention preferably in amounts of 0.1 to 3% by weight, based on the entire application preparation.
  • Use in the form of the palmitic acid ester, the glucosides or phosphates can be preferred.
  • Use in combination with tocopherols may also be preferred.
  • Vitamin E tocopherols, especially ⁇ -tocopherol.
  • Tocopherol and its derivatives which include in particular the esters such as acetate, nicotinate, phosphate and succinate, are preferably present in the agents according to the invention in amounts of 0.05-1% by weight, based on the entire application preparation.
  • Vitamin F usually means essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.
  • Vitamin H The compound (3aS, 4S, 6af?) - 2-oxohexahydrothienol [3,4-c] -imidazole-4-valeric acid is called vitamin H, but for which the trivial name biotin has now become established.
  • Biotin is present in the agents according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 0.001 to 0.01% by weight, in each case based on the entire application preparation.
  • the two-component agents according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, C, E and H.
  • Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinamide and biotin are particularly preferred.
  • the two-component agents according to the invention contain at least one plant extract.
  • extracts are usually produced by extracting the entire plant. In individual cases, however, it may also be preferred to produce the extracts exclusively from flowers and / or leaves of the plant.
  • the extracts from green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi and melon are particularly suitable.
  • Alcohols and mixtures thereof can be used as extractants for the production of the plant extracts mentioned.
  • alcohols lower alcohols such as ethanol and isopropanol, but in particular polyhydric alcohols such as ethylene glycol and propylene glycol, are preferred, both as the sole extracting agent and as a mixture with water.
  • Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.
  • the plant extracts can be used both in pure and in diluted form. If they are used in dilute form, they usually contain about 2 to 80% by weight of active substance and the extractant or extracting agent mixture used in their extraction as a solvent.
  • mixtures of several, in particular two, different plant extracts in the agents according to the invention may be preferred.
  • the two-component agents according to the invention contain at least one carboxylic acid as a care substance.
  • Short-chain carboxylic acids can be particularly advantageous in the sense of the invention.
  • Short-chain carboxylic acids and their derivatives for the purposes of the invention are understood to mean carboxylic acids which can be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and have a molecular weight of less than 750.
  • the short-chain carboxylic acids in the context of the invention can have one, two, three or more carboxy groups.
  • carboxylic acids having several carboxy groups preference is given to carboxylic acids having several carboxy groups, in particular di- and tricarboxylic acids.
  • the carboxy groups can be present in whole or in part as an ester, acid anhydride, lactone, amide, imidic acid, lactam, lactim, dicarboximide, carbohydrazide, hydrazone, hydroxam, hydroxime, amidine, amidoxime, nitrile, phosphonic or phosphate ester.
  • the carboxylic acids which can be used according to the invention can of course be substituted along the carbon chain or the ring structure.
  • the substituents of the carboxylic acids which can be used according to the invention include, for example, dCs-alkyl, C 2 -C 8 -alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C 2 -C 8 -hydroxyalkyl, C 2 -C 8- Hydroxyalkenyl, aminomethyl, C 2 -C 8 aminoalkyl, cyano, formyl, oxo, thioxo, hydroxy, mercapto, amino, carboxy or imino groups.
  • Preferred substituents are dC 8 alkyl, hydroxymethyl, hydroxy, amino and carboxy groups. Substituents in the ⁇ position are particularly preferred.
  • substituents are hydroxyl, alkoxy and amino groups, where the amino function can optionally be further substituted by alkyl, aryl, aralkyl and / or alkenyl radicals.
  • preferred carboxylic acid derivatives are the phosphonic and phosphate esters.
  • carboxylic acids which can be used according to the invention include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, propionic acid, sorbic acid, azelaic acid Crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoyl acid, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, 4,4'-carbonic acid -6,6 ' -binicot
  • NI in the Z stands for a linear or branched alkyl or alkenyl group with 4 to 12 carbon atoms, n for a number from 4 to 12 and one of the two groups X and Y for a COOH group and the other for hydrogen or one Methyl or ethyl radical, dicarboxylic acids of the general formula (Nl) which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids which formally form from the dicarboxylic acids of the formula (Nl) by the addition of a molecule of water to the double bond in the cyclohexene ring ,
  • Dicarboxylic acids of the formula (N-1) are known in the literature. For example, a manufacturing method can be found in US Pat. No. 3,753,968.
  • the dicarboxylic acids of the formula (NI) can be prepared, for example, by reacting polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder cyclization.
  • a polyunsaturated fatty acid is usually used as the dicarboxylic acid component.
  • the linoleic acid accessible from natural fats and oils is preferred.
  • Acrylic acid, but also, for example, methacrylic acid and crotonic acid are particularly preferred as the monocarboxylic acid component.
  • Diels-Alder reactions usually produce mixtures of isomers in which one component is in excess. According to the invention, these isomer mixtures can be used just like the pure compounds.
  • those dicarboxylic acids which differ from the compounds of the formula (Nl) by 1 to 3 methyl or ethyl substituents on the cyclohexyl ring or formally by addition of one of these compounds can also be used according to the invention Molecule of water are formed on the double bond of the cyclohexene ring.
  • the dicarboxylic acid (mixture) which results from the reaction of linoleic acid with acrylic acid has proven to be particularly effective according to the invention. It is a mixture of 5- and 6-carboxy-4-hexyl-2-cyclohexen-1-octanoic acid.
  • Such compounds are commercially available under the designations Westvaco Diacid 1550 Westvaco Diacid ® ® 1595 (manufacturer: Westvaco).
  • salts are the alkali, alkaline earth, zinc and ammonium salts, which in the context of the present application are also to be understood as the mono-, di- and trimethyl-, -ethyl- and -hydroxyethyl-ammonium salts.
  • acids which are neutralized with alkaline reacting amino acids such as, for example, arginine, lysine, ornithine and histidine, can very particularly preferably be used in the context of the invention.
  • 2-pyrrolidinone-5-carboxylic acid and its derivatives as the carboxylic acid.
  • Sodium, potassium, calcium, magnesium or ammonium salts are particularly preferred, in which the ammonium ion carries one to three Cr to C alkyl groups in addition to hydrogen.
  • the sodium salt is very particularly preferred.
  • the amounts used in the agents according to the invention are preferably 0.05 to 10% by weight, based on the entire application preparation, particularly preferably 0.1 to 5% by weight, and particularly preferably 0.1 to 3% by weight.
  • hydroxycarboxylic acids and in particular the dihydroxy, trihydroxy and polyhydroxycarboxylic acids as well as the dihydroxy, trihydroxy and polyhydroxydi, tri and polycarboxylic acids. It has been shown here that in addition to the hydroxycarboxylic acids, the hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters as well as polymeric hydroxycarboxylic acids and their esters can be very particularly preferred.
  • Preferred hydroxycarboxylic acid esters are, for example, full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid.
  • hydroxycarboxylic acid esters are esters of ⁇ -hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid.
  • Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols with 8-22 C atoms, for example fatty alcohols or synthetic fatty alcohols.
  • the esters of d 2 -C 15 fatty alcohols are particularly preferred.
  • Esters of this type are commercially available, eg under the trademark Cosmacol® ® EniChem, Augusta Industriale.
  • Particularly preferred polyhydroxy polycarboxylic acids are polylactic acid and poly-tartaric acid and their esters.
  • the two-component agents according to the invention contain at least one protein hydrolyzate and / or one of its derivatives as a care substance.
  • Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins).
  • protein hydrolyzates is also understood to mean total hydrolyzates and individual amino acids and their derivatives as well as mixtures of different amino acids.
  • polymers constructed from amino acids and amino acid derivatives are furthermore to be understood under the term protein hydrolyzates.
  • the latter include, for example, polyalanine, polyasparagine, polyserine, etc.
  • L-alanyl-L-proline polyglycine, glycyl-L-glutamine or D / L-methionine-S-methylsulfonium chloride.
  • ß-amino acids and their derivatives such as ß-alanine, anthranilic acid or hippuric acid can also be used according to the invention.
  • the molecular weight of the protein hydrolyzates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and very particularly preferably 75 to 20,000 daltons.
  • protein hydrolyzates of plant, animal, marine or synthetic origin can be used.
  • Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts.
  • Such products are, for example, under the trademarks Dehylan ® (Cognis), Promois ® (Interorgana), Collapuron ® (Cognis), Nutrilan ® (Cognis), Gelita-Sol ® (Deutsche Gelatine Fabriken Stoess & Co), Lexein ® (Inolex), Sericin (Pentapharm) and Kerasol ® (Croda) sold.
  • Silk is the fibers of the cocoon of the mulberry silk spinner (Bombyx mori L.).
  • the raw silk fiber consists of a double thread of fibroin.
  • Sericin holds this double thread together.
  • Silk consists of 70 - 80% by weight of fibroin, 19 - 28% by weight of sericin, 0.5 - 1% by weight of fat and 0.5 - 1% by weight of dyes and mineral components.
  • the essential components of the Sericin are with approx. 46% by weight hydroxy amino acids.
  • the sericin consists of a group of 5 to 6 proteins.
  • the essential amino acids of the Sericines are serine (Ser, 37% by weight), aspartate (Asp, 26% by weight), glycine (Gly, 17% by weight), alanine (Ala), leucine (Leu) and tyrosine (Tyr) ,
  • the water-insoluble fibroin is one of the skieroproteins with a long-chain molecular structure.
  • the main components of fibroin are glycine (44% by weight), alanine (26% by weight), and tyrosine (13% by weight).
  • Another essential structural feature of fibroin is the hexapeptide sequence Ser-Gly-Ala-Gly-Ala-Gly.
  • the positive properties of the silk protein derivatives from sericin and fibroin are known per se in the literature.
  • the Pentapharm sales brochure describes the cosmetic effects of Sericine on the skin as soothing, hydrating and film-forming.
  • the effect of a fibroin derivative is described, for example, in DE 31 39 438 A1 as nourishing and nourishing for the hair.
  • DE 102 40 757 A1 when sericin and fibroin or their derivatives and / or hydrolyzates are used simultaneously, a synergistic increase in the positive effects of the silk proteins and their derivatives can also be achieved.
  • An active substance complex (A) consisting of the active substance (A1) selected from sericin, sericin hydrolyzates and / or their derivatives, and mixtures thereof, and an active substance (A2) selected from fibroin, and / or is therefore preferred in the two-component agent according to the invention as the silk protein hydrolyzate Fibroin hydrolyzates and / or their derivatives and / or mixtures thereof are used.
  • the active ingredient complex (A) used according to the invention significantly, in a synergistic manner, improves the above-described essential internal and external structural features and the strength and elasticity of human hair.
  • hydrolyzed and / or further derivatized sericin such as commercial products with the INCI names Sericin, Hydrolyzed Sericin, or Hydrolyzed Silk,
  • fibroin hydrolyzed and / or further derivatized fibroin, especially partially hydrolyzed fibroin, which contains the amino acid sequence Ser-Gly-Ala-Gly-Ala- Gly as the main component,
  • the two active ingredients (A1) and (A2) in a ratio of 10:90 to 70:30, in particular 15:85 to 50:50 and very particularly 20:80 to 40:60, based on their respective contents of active ingredient in the two-component agents according to the invention.
  • the derivatives of the hydrolysates of sericin and fibroin include both anionic and cationized protein hydrolyzates.
  • the protein hydrolysates of sericin and fibroin and the derivatives produced therefrom can be obtained from the corresponding proteins by chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis.
  • the hydrolysis of proteins usually results in a protein hydrolyzate with a molecular weight distribution of approximately 100 daltons up to several thousand daltons.
  • cationic Protein hydrolyzates of sericin and fibroin also understand quaternized amino acids and their mixtures.
  • the quaternization of the protein hydrolyzates or the amino acids is often carried out using quaternary ammonium salts such as, for example, N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides.
  • the cationic protein hydrolyzates can also be further derivatized.
  • inventively employable cationic protein hydrolysates and derivatives are under the INCI - names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 th Street, NW, Suite 300, Washington, DC 20036-4702) and commercially available products: Cocodimonium Hydroxypropyl Hydrolyzed Silk, Cocodimonium Hydroxypropyl Silk Amino Acids, Hydroxyproypltrimonium Hydrolyzed Silk, Lauryldimonium Hydroxypropyl Hydrolyzed Silk, Steardimonium Hydroxypropyl Hydrolyzed Silk, Quatemiurn-79 Hydrolyzed Silk.
  • anionic protein hydrolyzates and derivatives according to the invention are those under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 th Street, NW, Suite 300 , Washington, DC 20036-4702) and commercially available products: Potassium Cocoyl Hydrolyzed Silk, Sodium Lauroyl Hydrolyzed Silk or Sodium Stearoyl Hydrolyzed Silk.
  • typical examples of the derivatives of sericin and fibroin which can be used according to the invention are the products commercially available under the INCI names: ethyl ester of hydrolyzed silk and hydrolyzed silk PG-propyl methylsilanediol.
  • Palmitoyl Oligopeptide Palmitoyl Pentapeptide-3, Palmitoyl Pentapeptide-2, Acetyl Hexapeptide-1, Acetyl Hexapeptide-3, Copper Tripeptide-1, Hexapeptide-1 , Hexapeptide-2, MEA-Hydrolyzed Silk.
  • the effect of the active ingredient complex (A) according to the invention can be further increased by adding fatty substances.
  • Fat substances are to be understood as meaning fatty acids, fatty alcohols, natural and synthetic waxes, which can be present both in solid form and in liquid form in aqueous dispersion, and natural and synthetic cosmetic oil components.
  • protein hydrolysates of plant origin e.g. B. soy, almond, pea, potato and wheat protein hydrolyzates.
  • Such products are, for example, under the trademarks Giuadin ® (Cognis), DiaMin ® (Diamalt), Lexein ® (Inolex), Hydrosoy ® (Croda), Hydrolupin ® (Croda), Hydrosesarne ® (Croda), Hydrotritium ® (Croda) and Crotein ® (Croda) available.
  • amino acid mixtures obtained in some other way can optionally be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products. Such products are sold for example under the names Lamepon ® (Cognis), Lexein ® (Inolex), Crolastin ® (Croda), Crosilk ® (Croda) or Crotein ® (Croda).
  • the protein hydrolyzates in the two-component compositions according to the invention are, for example, in concentrations from 0.01% by weight to 20% by weight, preferably from 0.05% by weight to 15% by weight and very particularly preferably in amounts of 0.05% by weight. % up to 5% by weight, each based on the entire application preparation.
  • the preparations according to the invention contain ectoin or ectoin derivatives, allantoin, taurine and / or bisabolol as a care substance.
  • R 10 represents a hydrogen atom, a branched or unbranched d - C 4 -alkyl radical or a C 2 - C 4 -hydroxyalkyl radical,
  • R 11 stands for a hydrogen atom, a group -CO OR 14 or a group - CO (NH) R 14 , where R 4 stands for a hydrogen atom, a d-, - C 4 -alkyl radical, an amino acid radical, a dipeptide or a tripeptide radical can stand
  • R 12 and R 13 independently of one another represent a hydrogen atom, a d - C 4 alkyl radical or a hydroxyl group, with the proviso that both radicals may not simultaneously represent a hydroxyl group, and n represents an integer from 1 to 3.
  • Suitable physiologically tolerable salts of the general compounds of the formula (IVa) or (IVb) are, for example, the alkali, alkaline earth, ammonium, triethylamine or tris (2-hydroxyethyl) amine salts and those which result from the reaction of compounds according to the formula (IVa) or (IVb) with inorganic and organic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, branched or unbranched, substituted or unsubstituted (for example by one or more hydroxyl groups) C 1 - C 4 - mono- or dicarboxylic acids, aromatic carboxylic acids and sulfonic acids such as acetic acid, citric acid, benzoic acid, maleic acid, fumaric acid, tartaric acid and p-toluenesulfonic acid.
  • inorganic and organic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, branched or unbranched, substituted or unsubstit
  • physiologically compatible salts are the Na, K, Mg and Ca and ammonium salts of the compounds of the formula (IVa) or (IVb), and the salts which are formed by reacting compounds of the formula (IVa ) or (IVb) with hydrochloric acid, acetic acid, citric acid and benzoic acid.
  • isomeric or stereoisomeric forms of the compounds of the formula (IVa) or (IVb) are taken to mean all optical isomers, diastereomers, racemates, zwitterions, cations or mixtures thereof.
  • amino acid describes the stereoisomeric forms, e.g. D and L forms of the following compounds understood:
  • arginine aspartic acid, glutamine, glutamic acid, beta-alanine, ⁇ -aminobutyrate, N ⁇ -Acetyllysin, N ⁇ -Acetylornitin, N ⁇ -Acetyldiaminobutyrat, N ⁇ -Acetyldiaminobutyrat, histidine, isoleucine, leucine, methionine, phenylalanine, serine, Threonine and tyrosine.
  • L-amino acids are preferred.
  • Amino acid residues are derived from the corresponding amino acids.
  • amino acid residues are preferred: Gly, Ala, Ser, Thr, Val, ⁇ -Ala, ⁇ -aminobutyrate, Asp, Glu, Asn, Aln, N ⁇ -acetyllysine, N ⁇ - acetylornithine, N ⁇ -acetyldiaminobutyrate, N ⁇ - Acetyldiaminobutyrat.
  • the shorthand notation of the amino acids was done according to the commonly used notation.
  • the di- or tripeptide residues are acid amides and break down into 2 or 3 amino acids during hydrolysis.
  • the amino acids in the di- or tripeptide residue are connected to one another by amide bonds.
  • Ci - C 4 alkyl groups in the compounds according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
  • Preferred alkyl groups are methyl and ethyl, methyl is a particularly preferred alkyl group.
  • Preferred C 2 -C 4 -hydroxyalkyl groups are the groups 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; 2-Hydroxyethyl is a particularly preferred hydroxyalkyl group.
  • the two-component agents according to the invention preferably contain these care substances in amounts of 0.001 to 2, in particular 0.01 to 0.5% by weight, in each case based on the entire application preparation.
  • the preparation (B) contains at least one mono- or oligosaccharide as a care substance.
  • Both monosaccharides and oligosaccharides such as cane sugar, milk sugar and raffinose, can be used.
  • the use of monosaccharides is preferred according to the invention.
  • Suitable pentoses and hexoses are, for example, ribose, arabinose, xylose, lyxose, allose, old rose, glucose, mannose, gulose, idose, galactose, talose, fucose and fructose.
  • Arabinose, glucose, galactose and fructose are preferred Carbohydrates;
  • Glucose is very particularly preferably used, which is suitable both in the D- (+) - or L - (-) configuration or as a racemate.
  • sugar acids are gluconic acid, glucuronic acid, sugar acid, mannosugaric acid and mucic acid.
  • Preferred sugar alcohols are sorbitol, mannitol and duicit.
  • Preferred glycosides are the methyl glucosides.
  • the mono- or oligosaccharides used are usually obtained from natural raw materials such as starch, they usually have the configurations corresponding to these raw materials (e.g. D-glucose, D-fructose and D-galactose).
  • the monosaccharides or oligosaccharides are preferably present in the hair treatment compositions according to the invention in an amount of 0.1 to 8% by weight, particularly preferably 1 to 5% by weight, based on the entire application preparation.
  • the two-component agent according to the invention contains at least one silicone oil and / or one silicone gum as a care substance.
  • Silicones or silicone gums suitable according to the invention are in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated, quaternized or also anionic derivatives.
  • silicones examples include: - Oligomeric polydimethylcyclosiloxanes (INCI name: Cyclomethicone), in particular the tetramer and the pentamer compound, which are sold as commercial products DC 344 and DC 345 by Dow Corning, - Hexamethyl-disiloxane (INCI name: Hexamethyldisiloxane ), e.g. B. the product sold under the name Abil ® K 520, - Polydimethylsiloxane (INCI name: Dimethicone), z. B. the products sold under the name DC 200 by Dow Corning, - Polyphenylmethylsiloxane (INCI name: Phenyl Trimethicone), z. B.
  • the preparations according to the invention contain a combination of a volatile and a non-volatile silicone.
  • Volatile in the sense of the invention are those silicones which have a volatility which is equal to or greater than the volatility of the cyclic, pentameric dimethylsiloxane.
  • Such combinations are also available as commercial products (eg Dow Corning® 1401, Dow Corning® 1403 and Dow Corning® 1501, in each case mixtures of a cyclomethicone and a dimethiconol).
  • preparation (B) contains a dialkylpolysiloxane or one of its derivatives as a care substance.
  • the alkyl groups are preferably methyl, ethyl, i-propyl and n-propyl.
  • Dimethylpolysiloxane or one of its derivatives is particularly preferably used.
  • the derivatives of dimethylpolysiloxane which are amino-functional are preferred.
  • a very particularly preferred derivative is commercially available under the INCI name Amodimethicone.
  • the preparations according to the invention preferably contain the silicones in amounts of 0.01-10% by weight, in particular 0.1-5% by weight, based on the entire application preparation.
  • preparation (B) contains at least one lipid as a care substance.
  • Lipids suitable according to the invention are phospholipids, for example soy lecithin, egg lecithin and cephaline, and also the substances known under the INCI names linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate and Stearamidopropyl PG-Dimonium Chloride Phosphate. These are sold, for example, by Mona under the trade names Phospholipid EFA ® , Phospholipid PTC ® and Phospholipid SV ® .
  • the preparations according to the invention preferably contain the lipids in amounts of 0.01-10% by weight, in particular 0.1-5% by weight, based on the entire application preparation.
  • the preparation (B) contains at least one oil body as a care substance.
  • the natural and synthetic cosmetic oil bodies include, for example:
  • oils examples include sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach seed oil and the liquid components of coconut oil.
  • Other triglyceride oils such as the liquid portions of beef tallow and synthetic triglyceride oils are also suitable.
  • Ester oils are understood to be the esters of C 6 -C 30 fatty acids with C 2 -C 30 fatty alcohols. The monoesters of fatty acids with alcohols having 2 to 24 carbon atoms are preferred.
  • fatty acid moieties in the esters are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, Isotridecan- acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, Behenic acid and erucic acid, as well as their technical mixtures, which occur, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or in the directing of unsaturated fatty acids.
  • fatty alcohol alcohol parts in the ester oils are isopropyl alcohol, capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaolyl alcohol, elaol alcohol, elaol alcohol, elaol alcohol , Gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the directing of unsaturated fatty alcohols.
  • isopropyl pylmyristat (Rilanit ® IPM), isononanoic acid C16-18 alkyl ester (Cetiol ® SN), 2-Ethylhes ⁇ ylpalmitat (Cegesoft ® 24), stearic acid-2-ethylhexyl ester (Cetiol ® 868), cetyl oleate, Gtycerintrica - prylate, coconut fatty alcohol caprinate / caprylate (Cetiol ® LC), n-butyl stearate, olerlerucate (Cetiol ® J 600), isopropyl palmitate (Rilanit ® IPP), oleyl oleate (Cetiol ® ), lauric acid hexyl ester (Cetiol ® A), Di-n-butyl adipate (C
  • Dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecylacelate as well as diol esters such as ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di (2- ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate, neopentyl glycol dicaprylate, symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or Dicaprylyl carbonate (Cetiol ® CC),
  • the partial glycerides preferably follow the formula (D4-I),
  • R 1 in the R 1 , R 2 and R 3 independently of one another represent hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups is an acyl radical and at least one of these groups stands for hydrogen.
  • the sum (m + n + q) represents 0 or numbers from 1 to 100, preferably 0 or 5 to 25.
  • R 1 preferably represents an acyl radical and R 2 and R 3 represents hydrogen and the sum (m + n + q) is 0.
  • Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linoleic acid , Elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Oleic acid monoglycerides are preferably used.
  • the amount of natural and synthetic cosmetic oil bodies used in the two-component compositions according to the invention is usually 0.1-30% by weight, based on the overall application preparation, preferably 0.1-20% by weight, and in particular 0.1-15% by weight. %.
  • preparation (B) contains an enzyme as a care substance.
  • Enzymes which are particularly preferred according to the invention are selected from a group which is formed from proteases, lipases, transglutaminase, oxidases and peroxidases.
  • the two-component agents according to the invention contain at least one pearl extract.
  • Pearls of mussels consist essentially of inorganic and organic calcium salts, trace elements and proteins. Pearls can easily be obtained from cultivated shells. The mussels can be cultivated in both fresh water and sea water. This can affect the ingredients of the pearls. According to the invention, a pearl extract is preferred which comes from mussels cultivated in sea or salt water.
  • the pearls consist largely of aragonite (calcium carbonate), conchiolin and an albuminoid. The latter components are proteins. Pearls also contain magnesium and sodium salts, inorganic silicon compounds and phosphates.
  • the pearls are pulverized to produce the pearl extract.
  • the powdered beads are then extracted using the usual methods.
  • Water, alcohols and mixtures thereof can be used as extractants for the preparation of the pearl extracts.
  • Water is understood to mean both demineralized water and sea water.
  • alcohols lower alcohols such as ethanol and isopropanol, but in particular polyhydric alcohols such as glycerol, diglycerol, triglycerol, polyglycerol, ethylene glycol, propylene glycol and butylene glycol, are preferred, both as the sole extracting agent and as a mixture with demineralized water or sea water.
  • Pearl extracts based on water / glycerin mixtures have proven to be particularly suitable.
  • the pearl proteins can be largely in their native state or already partially or largely as protein hydrolyzates.
  • a pearl extract in which the conchiolin and albuminoid are already partially hydrolyzed is preferred.
  • the essential amino acids of these proteins are glutamic acid, serine, alanine, glycine, aspartic acid and phenylalanine.
  • the pearl extract is additionally enriched with at least one or more of these amino acids.
  • the pearl extract is enriched with glutamic acid, serine and leucine.
  • a preferred extract contains organic and / or inorganic calcium salts as well as magnesium and sodium salts, inorganic silicon compounds and / or phosphates.
  • a very preferred pearl extract contains at least 75%, preferably 85%, particularly preferably 90% and very particularly preferably 95% of all ingredients of the naturally occurring pearls. Examples of pearl extracts usable according to the invention are the commercial products Pearl Protein Extract BG ® or Crodarom ® Pearl.
  • the pearl extracts described above are preferably contained in an amount of at least 0.01 to 20% by weight. Amounts of the extract of 0.01 to 10% by weight are preferably used, very particularly preferably amounts of 0.01 to 5% by weight, based on the total two-component agent.
  • the scope of the present invention also includes all embodiments in which the preparation (B) contains a plurality of care substances from different groups.
  • the two-component agent according to the invention is assembled in different chambers of a multi-chamber tube.
  • the multi-chamber tube is preferably a two-chamber tube, a first chamber receiving the preparation (A) and a second chamber receiving the preparation (B).
  • a multi-chamber tube which has more than two chambers, for example three or four chambers.
  • preparation (A) and / or preparation (B) can be distributed over several chambers of the multi-chamber tube, whereby it must of course be ensured that only preparation (A) or preparation (B) is in a particular chamber.
  • two-chamber tubes are already known in the prior art.
  • the tubes have two separate chambers, which are designed as nested tubes. These define the inner and the outer chamber and end in the common head or outlet area.
  • the head area is designed in such a way that the two preparations exit the tube together as soon as pressure is exerted on it.
  • the design of the head area determines the stripe pattern in which the preparations emerge from the tube.
  • the known commercially available tubes have an equal ratio of the volumes of the inner tube to the outer tube and thus a mixing ratio of 50:50. For products whose two phases have to be kept separate and whose mixing If the ratio deviates from the conventional value of 50:50, the known tubes are not suitable.
  • the two-component agents according to the invention are preferably assembled in a two-chamber tube which has an inner and an outer chamber, both of which end in a common head region (outlet region).
  • the head area is designed in such a way that the two preparations exit the tube together as soon as pressure is exerted on it. The design of this head area determines the pattern in which the preparations emerge from the tube.
  • the selection of the volumes of the individual chambers depends on the desired ratio of the volumes of preparation (A) and preparation (B) in the two-component agent.
  • the preferably used two-chamber tube is characterized in particular by a special design of the outlet area.
  • the ratio of the chamber volumes is reflected here in the cross sections of the paths defined for the partial flows.
  • the partial flow of a preparation can have several parallel branch flows.
  • separating agents can divide the cross-section of the through-channel into at least almost the ratio into two or more partial streams. It should be noted that it is advantageous for the function of the two-chamber tubes if the different components present in the respective tube chambers each have approximately the same viscosity.
  • the invention is in no way limited in principle with regard to the pattern with which the preparations emerge from the tube, it can be preferred according to the invention if the first preparation emerges as the main strand and the second preparation forms several strips running along this main strand.
  • the invention should also not be restricted with regard to the number of these strips. According to the invention, however, a number of 2 to 4 strips can be particularly preferred for reasons of application technology.
  • the preparation (A) forms the strips, while the preparation (B) forms the main strand, and in a second embodiment, the preparation (B) forms the strips, while the preparation (A) forms the main strand.
  • the two preparations together form the main strand together.
  • the outlet strand can consist of an inner region, formed from a first preparation, and an outer region, formed from the second preparation, the preparations also forming the outlet strand according to their arrangement in the tube.
  • the ratio of the amount of preparation (A) to the amount of preparation (B) according to the invention is preferably in a range from 1: 2 to 5: 1, a range from 1: 1 to 3: 1 is particularly preferred according to the invention.
  • the present invention is intended to encompass any distribution of the chambers within the tube.
  • the two individual chambers can be arranged next to one another in an outer shell.
  • the two-chamber tube consists of an inner tube which is completely surrounded by an outer tube. This embodiment is characterized by an optimally constant dosage of the two preparations.
  • every distribution of the preparations to the chambers of the tube is to be encompassed according to the invention, it can be particularly preferred if the preparation (A) is in the outer tube and the preparation (B) is in the inner tube.
  • the two-chamber tube is preferably made of a material that is suitable for packaging toning and coloring agents of this type.
  • Laminated aluminum has proven particularly suitable according to the invention both for the outer walls and for the inner walls.
  • tubes made of plastic laminate (PE, PET, PP) or plastic coextrudates (PE, PET, PP) are also conceivable.
  • the material of the inner tube can be selected independently of the material of the outer tube.
  • a tube in which the inner tube is made of aluminum laminate, which may also be protected with a lacquer, and the outer tube is made of either aluminum laminate or plastic laminate has proven to be particularly preferred according to the invention.
  • aluminum laminate means an aluminum layer coated with plastic. It is particularly advantageous if the shoulder area of the outer tube is reinforced with round blanks which have particularly good barrier properties. It is advantageous to incorporate aluminum into the material of the round blanks.
  • preparations (A) and (B) can also contain all active ingredients, additives and auxiliaries known for such preparations.
  • the colorants contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.
  • Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms.
  • anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms.
  • the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C 8 -C 22 carboxylic acids, such as oleic acid, stearic acid , Isostearic acid and palmitic acid.
  • Non-ionic surfactants contain z.
  • B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group.
  • Such compounds are, for example, adducts of 2 to 30 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group, C 12 -C 22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol, C 8 -C 22 alkyl mono- and oligoglycosides and their ethoxylated analogues, and adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.
  • Preferred nonionic surfactants are alkyl polyglycosides of the general formula R 1 0- (Z) ⁇ . These connections are characterized by the following parameters.
  • the alkyl radical R 1 contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.
  • the alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R 1 .
  • these compounds are made from natural fats and oils or mineral oils.
  • the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.
  • R 1 essentially consists of C 8 and C 10 alkyl groups, essentially from C 12 and C 1 alkyl groups, essentially from C 8 to C 16 alkyl groups or essentially from C 12 - to C 16 alkyl groups.
  • Any mono- or oligosaccharides can be used as the sugar building block Z.
  • Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used.
  • sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose.
  • Preferred sugar components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.
  • alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.
  • the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair.
  • the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention.
  • the alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.
  • zwitterionic surfactants can be used, in particular as co-surfactants.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO H - or -S0 3 (_) group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethyl- ammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.
  • Ampholytic surfactants are also particularly suitable as co-surfactants.
  • Ampholytic surfactants are surface-active compounds which, in addition to a C 8 -C 18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -S0 3 H group in the molecule and are capable of forming internal salts are.
  • ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylamino propionic acid and alkylamino acetic acid each with about 8 to 18 carbon atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and C 12-18 acyl sarcosine.
  • the cationic surfactants used are, in particular, those of the quaternary ammonium compound, esterquat and amidoamine type.
  • Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds.
  • the long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
  • Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element.
  • Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines.
  • Such products are sold, for example, under the trademarks Stepantex ® , Dehyquart ® and Armocare ® .
  • the alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines.
  • An inventively particularly suitable compound from this group of substances that available under the name Tegoamid ® S 18 commercially stearamidopropyldimethylamine is dimethylamine.
  • the quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.
  • cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).
  • a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride”.
  • the compounds with alkyl groups used as surfactant can each be uniform substances. However, it is usually preferred in manufacturing These substances are based on natural vegetable or animal raw materials, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.
  • both products with a "normal” homolog distribution and those with a narrowed homolog distribution can be used.
  • “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates.
  • narrow homolog distributions are obtained if, for example, hydrotaicites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.
  • the colorants according to the invention can contain further active ingredients, auxiliaries and additives, such as, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysilammonones, with quaternary chloride groups, with quaternary chloride groups , Acrylamide-dimethyldiallyl-ammonium chloride copolymers, with diethyl sulfate quaternized dimethylamino-ethyl methacrylate-vinyl pyrrolidone copolymers, vinyl pyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers / such as acrylamidyl amide
  • - Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, for.
  • B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,
  • Protein hydrolyzates in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,
  • Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, active substances that improve fiber structure, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2 alkylimidazolinium methosulfate defoamers such as silicones, dyes for coloring the agent,
  • Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
  • Substances for adjusting the pH such as customary acids, in particular edible acids and bases,
  • Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts as well as bisabolol, vitamins, provitamins and vitamin precursors, in particular those of groups A, B 3 , B 5 , B ⁇ , C, E, F and H,
  • Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root.
  • Cholesterol Cholesterol
  • Consistency agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides, complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids, Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
  • Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, preservatives, stabilizers for hydrogen peroxide and other oxidizing agents,
  • blowing agents such as propane-butane mixtures, N 2 0, dimethyl ether, C0 2 and air,
  • Preparations (A) and (B) preferably contain the components essential to the invention in a suitable aqueous, alcoholic or aqueous-alcoholic carrier.
  • a suitable aqueous, alcoholic or aqueous-alcoholic carrier are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair.
  • aqueous-alcoholic solutions are understood to mean aqueous solutions containing 3 to 70% by weight of a dC 4 alcohol, in particular ethanol or isopropanol.
  • the agents according to the invention can additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred.
  • the two-component agents according to the invention can contain a reducing agent.
  • preferred reducing agents according to the invention are sodium sulfite, ascorbic acid, thioglycolic acid and their derivatives, sodium thionite, alkali metal citrate salts and N-acetyl-L-cysteine.
  • Particularly preferred reducing agents are alkali metal citrate salts, in particular sodium citrate, and N-acetyl-L-cysteine.
  • N-acetyl-L-cysteine is a very particularly preferred reducing agent.
  • the agents according to the invention can furthermore contain alkalizing agents, usually alkali or alkaline earth metal hydroxides, ammonia or organic amines.
  • Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1, 3-propanediol, 2-amino-2 - methylbutanol and triethanolamine as well as alkali and alkaline earth metal hydroxides.
  • Monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanediol are particularly preferred in this group.
  • the use of ⁇ -amino acids such as ⁇ -aminocaproic acid as an alkalizing agent is also possible.
  • Pearlescent pigments are often used for this purpose.
  • Pearlescent pigments preferred according to the invention are natural pearlescent pigments such as e.g. Fish silver (guanine / hypoxanthine mixed crystals from fish scales) or mother-of-pearl (from ground mussel shells), monocrystalline pearlescent pigments such as Bismuth oxychloride and pearlescent pigments based on mica or mica / metal oxide.
  • monocrystalline pearlescent pigments such as Bismuth oxychloride and pearlescent pigments based on mica or mica / metal oxide.
  • the latter pearlescent pigments are provided with a metal oxide coating.
  • the pearlescent pigments sheen and optionally additional color effects are achieved in the two-component agents according to the invention.
  • the coloring due to the pearlescent pigments used in the two-component agents does not influence the color result of the coloring of the keratin fibers.
  • Pearlescent pigments based on mica and on mica / metal oxide are also preferred according to the invention.
  • Mica is one of the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite.
  • the mica predominantly muscovite or phlogopite, is coated with a metal oxide. Suitable metal oxides include Ti0 2 , Cr 2 0 3 and Fe 2 0 3 .
  • Corresponding coatings and interference luster pigments are obtained as pearlescent pigments according to the invention by means of a corresponding coating.
  • the pearlescent pigments which can be used according to the invention can furthermore contain a color pigment which is not derived from a metal oxide.
  • the grain size of the preferably used pearlescent pigments is preferably between 1.0 and 100 ⁇ m, particularly preferably between 5.0 and 60.0 ⁇ m.
  • pearlescent pigments are pigments which are marketed by the Merck company under the trade name Colorona ® , the pigments Colorona ® red-brown (47-57% by weight Muscovit Mica (KH 2 (AISi0 4 ) 3 ), 43-50% by weight % Fe 2 0 3 (INCI: Iran Oxides Cl 77491), ⁇ 3% by weight Ti0 2 (INCI: Titanium Dioxide Cl 77891), Colorona ® Blackstar Blue (39-47% by weight Muscovit Mica (KH 2 (AISi0 4 .) 3), 53-61% by weight of Fe 3 0 4 (INCI: Iran oxide Cl 77499)), Colorona ® Fine Siena (35-45% by weight of muscovite mica (KH 2 (AISi0 4) 3), 55-65.
  • Colorona ® the pigments Colorona ® red-brown (47-57% by weight Muscovit Mica (KH 2 (AISi0 4 ) 3 ), 43-50% by weight
  • pearlescent pigments which can be used in the two-component compositions according to the invention, reference is also expressly made to the monographs Inorganic Pigments, Chemical technology review No. 166, 1980, pages 161-173 (ISBN 0-8155-0811-5) and Industrial inorganic Pigments, 2nd edition, Weinheim , VCH, 1998, pages 211-231.
  • the actual oxidative coloring of the fibers can basically be done with atmospheric oxygen.
  • a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired.
  • Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents.
  • the oxidation coloring agent can also be applied to the hair together with a catalyst which activates the oxidation of the dye precursors, for example by atmospheric oxygen.
  • catalysts are, for example, metal ions, iodides, quinones or certain enzymes.
  • Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2 0 Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ .
  • Zn 2 ⁇ Cu 2+ and Mn 2+ are particularly suitable.
  • the metal ions can be used in the form of any physiologically acceptable salt or in the form of a complex compound.
  • Preferred salts are the acetates, sulfates, halides, lactates and tartrates.
  • Suitable enzymes are e.g. Peroxidases, which can significantly increase the effects of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and thus bio-catalytically activate the oxidation of the dye precursors.
  • Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific for this, e.g. Pyranose oxidase and e.g.
  • D-glucose or galactose glucose oxidase and D-glucose, glycerin oxidase and glycerin, pyruvate oxidase and pyruvic acid or their salts, - alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and their salts, Tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and amino acids.
  • the actual hair dye is expediently prepared immediately before use by mixing the preparation of an oxidizing agent with the preparations (A) and (B) applied from the tube.
  • the resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12.
  • the information on the pH value within the scope of the present disclosure is to be understood as the pH value at 25 ° C.
  • the use of hair dyes in an alkaline environment is particularly preferred. Application temperatures can range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes, the hair dye is rinsed out of it staining hair removed. Washing with a shampoo is not necessary if a carrier with a high tenside content, such as a coloring shampoo, has been used.
  • the two-component agent can also be applied to the hair and massaged in without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if necessary after an intermediate rinse. After a further exposure time of 10 to 20 minutes, rinsing is then carried out and, if desired, re-shampooing.
  • the corresponding agent is adjusted to a pH of about 4 to 7.
  • air oxidation is initially aimed for, the agent applied preferably having a pH of 7 to 10. In the subsequent accelerated postoxidation, the use of acidified peroxidisulfate solutions as the oxidizing agent can be preferred.
  • Preparations (A) and (B) of the two-component agent according to the invention preferably have viscosities in the range from 2,000 to 200,000 mPas, in particular from 5,000 to 50,000 mPas (Brookfield viscometer, spindle no. 4, 20 rpm, 20 ° C.) on. This ensures that the two-component agent has good miscibility and nevertheless the exit pattern has sufficient stability.
  • a second object of the present invention is a process for dyeing keratin fibers, in particular human hair, wherein a two-component agent according to the invention is pressed out of the tube, mixed with an oxidizing agent preparation, the resulting application preparation is applied to the fibers and again after an exposure time is rinsed off.
  • Coloring The coloring creams A to I were each made up in a 3: 1 ratio with the care components B1 and B2 or in a 1: 1 ratio with the care components B3 and B4 in a two-chamber tube.
  • the two-component agent was placed in a two-chamber tube in an application bowl and mixed there with the above-mentioned oxidizing agent preparation.
  • the resulting application preparation was then applied to human hair (Kerling natural white), massaged in there, left to act at room temperature for 30 min and then rinsed out. After drying the hair, intense shades of blonde, red or blue-black were achieved.
  • Acrysol ® 22 acrylic polymer (approx. 29.5 - 30.5% solids in water; INCI name: Acrylates / Steareth-20 methacrylate copolymer)
  • Akypo Soft 45 NV ® Lauryl alcohol-4.5-EO-acetic acid sodium salt (at least 21% active substance content; INCI name: Sodium Laureth-6 Carboxylate) (Chem-Y) Dehyquart ® A-CA trimethylhexadecylammonium chloride (approx.
  • Edenor ® C14 myristic acid (INCI name: MYRISTIC ACID) (Cognis) Eumulgin ® B 1 cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis Eumulgin ® B2 cetylstearyl alcohol with approx.
  • Phopholipid ® EFA (INCI name: Linoleamidopropyl PG-Dimonium Chloride Phosphate) (Uniqema)
  • Plantacare ® 12O0 UP C12-16-fatty alcohol-1.4-glucoside (approx. 50-53% active substance content; INCI name: Lauryl Glucoside, Aqua (Water)) (Cognis)
  • Texapon ® N28 lauryl ether sulfate sodium salt (at least 26.5% active substance content; INCI name: Sodium Laureth Sulfate) (Cognis)
  • Texapon ® NSO lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (Cognis)
  • Turpinal ® SL 1-hydroxyethane-1, 1-diphosphonic acid (approx. 58 - 61% active substance content; INCI name : Etidronic Acid, Aqua (Water)) (Solutia)

Abstract

The invention relates to two-component agents which are used to colour keratin fibres. Said agents comprise a first preparation (A) containing at least one oxidation colorant precursor, and a second preparation (B) containing at least one care product. The two preparations are made separately from each other in the chamber of a tube having two chambers. The inventive two-component agents are characterised in that they have excellent care characteristics and colouring properties in addition to high stability.

Description

"Pflegendes Oxidationsfärbemittel in Tube" "Nourishing Oxidation Colorant in a Tube"
Die vorliegende Erfindung betrifft ein Zweikomponentenmittel zur Färbung keratinischer Fasern, das in einer Zweikammertube konfektioniert ist, eine entsprechende Zweikammertube sowie ein Verfahren zur Färbung keratinischer Fasern mit Hilfe dieser Mittel.The present invention relates to a two-component agent for coloring keratin fibers, which is assembled in a two-chamber tube, a corresponding two-chamber tube and a method for dyeing keratin fibers using these agents.
Menschliches Haar wird heute in vielfältiger Weise mit haarkosmetischen Zubereitungen behandelt. Dazu gehören etwa die Reinigung der Haare mit Shampoos, die Pflege und Regeneration mit Spülungen und Kuren sowie das Bleichen, Färben und Verformen der Haare mit Färbemitteln, Tönungsmitteln, Wellmitteln und Stylingpräparaten. Dabei spielen Mittel zur Veränderung oder Nuancierung der Farbe des Kopfhaares eine herausragende Rolle.Today human hair is treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with dyes, tinting agents, waving agents and styling preparations. Means for changing or shading the color of the head hair play an outstanding role.
Für temporäre Färbungen werden üblicherweise Färbe- oder Tönungsmittel verwendet, die als färbende Komponente sogenannte Direktzieher enthalten. Hierbei handelt es sich um Farbstoffmoleküle, die direkt auf das Haar aufziehen und keinen oxidativen Prozess zur Ausbildung der Farbe benötigen. Zu diesen Farbstoffen gehört beispielsweise das bereits aus dem Altertum zur Färbung von Körper und Haaren bekannte Henna. Diese Färbungen sind gegen Shampoonieren in der Regel deutlich empfindlicher als die oxidativen Färbungen, so dass dann sehr viel schneller eine vielfach unerwünschte Nuancenverschiebung oder gar eine sichtbare "Entfärbung" eintritt.Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much undesired shift in nuances or even a visible "discoloration" occurs much more quickly.
Für dauerhafte, intensive Färbungen mit entsprechenden Echtheitseigenschaften werden sogenannte Oxidationsfärbemittel verwendet. Solche Färbemittel enthalten üblicherweise Oxidationsfarbstoffvorprodukte, sogenannte Entwicklerkomponenten und Kupplerkomponenten. Die Entwicklerkomponenten bilden unter dem Einfluss von Oxidationsmitteln oder von Luftsauerstoff untereinander oder unter Kupplung mit einer oder mehreren Kupplerkomponenten die eigentlichen Farbstoffe aus. Die Oxidationsfärbemittel zeichnen sich durch hervorragende, lang anhaltende Färbeergebnisse aus. Für natürlich wirkende Färbungen muss üblicherweise eine Mischung aus einer größeren Zahl von Oxidationsfarb- stoffvorprodukten eingesetzt werden; in vielen Fällen werden weiterhin direktziehende Farbstoffe zur Nuancierung verwendet.So-called oxidation dyes are used for permanent, intensive dyeings with appropriate fastness properties. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components. The oxidation coloring agents are characterized by excellent, long-lasting coloring results. A mixture of a larger number of oxidation dye precursors usually has to be used for natural-looking dyeings; in many cases direct dyes are still used for shading.
Nicht zuletzt durch die starke Beanspruchung der Haare durch derartige farbverändernde Behandlungen, aber auch durch Dauerwellen, die Reinigung der Haare mit Shampoos und durch Umweltbelastungen, nimmt die Bedeutung von Pflegeprodukten mit möglichst langanhaltender Wirkung zu. Derartige Pflegemittel beeinflussen die natürliche Struktur und die Eigenschaften der Haare. So können anschließend an eine Behandlung mit einem Pflegemittel beispielsweise die Nass- und Trockenkämmbarkeit des Haares, der Halt, die Festigkeit und die Fülle des Haares optimiert sein oder die Haare vor erhöhtem Spliss geschützt sein.Not least because of the heavy demands placed on the hair by such color-changing treatments, but also by perms, cleaning the hair with shampoos and by environmental pollution, the importance of care products takes as much as possible long-lasting effect. Care products of this type influence the natural structure and properties of the hair. Following treatment with a care product, for example, the wet and dry combability of the hair, the hold, the strength and the fullness of the hair can be optimized or the hair can be protected from increased split ends.
Es ist daher seit langem üblich, die Haare einer speziellen Nachbehandlung zu unterziehen. Dabei werden, üblicherweise in Form einer Spülung, die Haare mit speziellen Wirkstoffen, beispielsweise quatemären Ammoniumsalzen oder speziellen Polymeren, behandelt. Durch diese Behandlung werden je nach Formulierung die Kämmbarkeit, der Halt und die Fülle der Haare verbessert und die Splissrate verringert.It has therefore long been customary to subject the hair to a special after-treatment. Here, usually in the form of a rinse, the hair is treated with special active ingredients, for example quaternary ammonium salts or special polymers. Depending on the formulation, this treatment improves the combability, hold and fullness of the hair and reduces the split rate.
Die zur Verfügung stehenden Wirkstoffe wirken im allgemeinen bevorzugt an der Haaroberfläche. So sind Wirkstoffe bekannt, welche dem Haar Glanz, Halt, Fülle, bessere Nass- oder Trockenkämmbarkeiten verleihen oder dem Spliss vorbeugen. Genauso bedeutend wie das äußere Erscheinungsbild der Haare ist jedoch der innere strukturelle Zusammenhalt der Haarfasern, der insbesondere bei oxidativen und reduktiven Prozessen wie Färbung und Dauerwellen stark beeinflusst werden kann. Es wurden in letzter Zeit auch Wirkstoffe vorgeschlagen, die dieser Änderung der inneren Struktur der Fasern nachhaltig entgegenwirken können.The active ingredients available generally act preferentially on the hair surface. Active ingredients are known which give hair shine, hold, fullness, better wet or dry combability or prevent split ends. However, just as important as the external appearance of the hair is the internal structural cohesion of the hair fibers, which can be greatly influenced in particular in oxidative and reductive processes such as coloring and perms. Active substances that can counteract this change in the internal structure of the fibers in the long term have also been proposed.
In jüngster Zeit wurden sogenannte Kombinationspräparate entwickelt, um den Aufwand der üblichen mehrstufigen Verfahren, insbesondere bei der direkten Anwendung durch Verbraucher, zu verringern. Diese Präparate enthalten neben den üblichen Komponenten zur Färbung der Haare, zusätzlich Wirkstoffe, die früher den Haarnachbehandlungsmitteln vorbehalten waren. Der Konsument spart somit einen Anwendungsschritt; gleichzeitig wird der Verpackungsaufwand verringert, da ein Produkt weniger gebraucht wird.In recent times, so-called combination preparations have been developed in order to reduce the effort of the usual multi-stage processes, particularly when used directly by consumers. In addition to the usual components for coloring the hair, these preparations also contain active ingredients which were formerly reserved for the hair aftertreatment agents. The consumer thus saves one application step; At the same time, the packaging effort is reduced because one product is used less.
Die bekannten Wirkstoffe weisen jedoch teilweise den Nachteil auf, dass sie in den Färbemitteln nicht stabil formuliert werden können.However, some of the known active ingredients have the disadvantage that they cannot be stably formulated in the colorants.
Es wurde nunmehr überraschenderweise gefunden, dass stabile Färbemittel mit einer hervorragenden Pflegewirkung erhalten werden können, wenn ein Mittel enthaltend mindestens ein Oxidationsfarbstoffvorprodukt und ein Mittel enthaltend mindestens eine Pflegekomponente getrennt voneinander in einer Zweikammertube konfektioniert werden. Ein erster Gegenstand der vorliegenden Erfindung sind daher Zweikomponentenmittel zur Färbung keratinischer Fasern, umfassend eine erste Zubereitung (A), enthaltend mindestens ein Oxidationsfarbstoffvorprodukt, und eine zweite Zubereitung (B), enthaltend mindestens einen Pflegestoff, wobei die beiden Zubereitungen getrennt voneinander in den Kammern einer Zweikammertube konfektioniert sind.It has now surprisingly been found that stable colorants with an excellent care effect can be obtained if an agent containing at least one oxidation dye precursor and an agent containing at least one care component are packaged separately from one another in a two-chamber tube. The present invention therefore firstly relates to two-component agents for dyeing keratin fibers, comprising a first preparation (A) containing at least one oxidation dye precursor and a second preparation (B) containing at least one care substance, the two preparations being separate from one another in the chambers Two-chamber tubes are made up.
Die erfindungsgemäßen Zweikomponentenmittel zeichnen sich durch eine hervorragende Pflege- und Färbeleistung und eine hohe Stabilität aus. Darüber hinaus ist gewährleistet, dass der Verbraucher die Komponenten im vom Hersteller geplanten Mischungsverhältnis appliziert. Auf diese Weise ist einerseits die Produktsicherheit erhöht und andererseits ist gewährleistet, dass das Produkt die gewünschte Leistung erbringt.The two-component agents according to the invention are notable for excellent care and coloring performance and high stability. It also ensures that the consumer applies the components in the mixing ratio planned by the manufacturer. In this way, on the one hand, product safety is increased and, on the other hand, it is guaranteed that the product achieves the desired performance.
In einer ersten bevorzugten Ausführungsform enthält die Zubereitung (A) mindestens eine Entwicklerkomponente. Als Entwicklerkomponenten werden üblicherweise primäre aromatische Amine mit einer weiteren, in para- oder ortho-Position befindlichen, freien oder substituierten Hydroxy- oder Aminogruppe, Diaminopyridinderivate, heterocyclische Hydrazone, 4-Aminopyrazolderivate sowie 2,4,5,6-Tetraaminopyrimidin und dessen Derivate eingesetzt.In a first preferred embodiment, preparation (A) contains at least one developer component. Primary aromatic amines with a further free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and their derivatives are usually used as developer components ,
Es kann erfindungsgemäß bevorzugt sein, als Entwicklerkomponente ein p-Phenylendi- aminderivat oder eines seiner physiologisch verträglichen Salze einzusetzen. Besonders bevorzugt sind p-Phenylendiaminderivate der Formel (E1)It can be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred
Figure imgf000004_0001
Figure imgf000004_0001
wobei G1 steht für ein Wasserstoffatom, einen C bis C4-Alkylrest, einen C bis C4- Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (C bis C )-Alkoxy- (d- bis C )-alkylrest, einen 4'-Aminophenylrest oder einen C bis C4-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist; G2 steht für ein Wasserstoffatom, einen C bis C -Alkylrest, einen C bis C4- Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (C bis C4)-Alkoxy- (C bis C )-alkylrest oder einen C bis C4-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist; G3 steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, lod- oder Fluoratom, einen d- bis C4-Alkylrest, einen C bis C4-Monohydroxyalkylrest, einen C2- bis C -Polyhydroxyalkylrest, einen C bis C4-Hydroxyalkoxyrest, einen C bis C4- Acetylaminoalkoxyrest, einen C bis C4- Mesylaminoalkoxyrest oder einen C bis C4- Carbamoylaminoalkoxyrest; G4 steht für ein Wasserstoffatom, ein Halogenatom oder einen Cr bis C4-Alkylrest oder wenn G3 und G4 in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.where G 1 represents a hydrogen atom, a C to C 4 alkyl radical, a C to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a (C to C) alkoxy- (d- to C) - alkyl radical, a 4'-aminophenyl radical or a C to C 4 alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical; G 2 represents a hydrogen atom, a C to C alkyl radical, a C to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a (C to C 4 ) alkoxy (C to C) alkyl radical or a C to C 4 alkyl radical which is substituted by a nitrogen-containing group; G 3 represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, ad- to C 4 -alkyl radical, a C to C 4 -monohydroxyalkyl radical, a C 2 - to C -polyhydroxyalkyl radical, one C to C 4 hydroxyalkoxy, a C to C 4 acetylaminoalkoxy, a C to C 4 mesylaminoalkoxy or a C to C 4 carbamoylaminoalkoxy; G 4 represents a hydrogen atom, a halogen atom or a C r to C 4 alkyl radical or if G 3 and G 4 are in the ortho position to one another, they can together form a bridging α, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group.
Beispiele für die als Substituenten in den erfindungsgemäßen Verbindungen genannten Cr bis C -Alkylreste sind die Gruppen Methyl, Ethyl, Propyl, Isopropyl und Butyl. Ethyl und Methyl sind bevorzugte Alkylreste. Erfindungsgemäß bevorzugte Cr bis C4- Alkoxyreste sind beispielsweise eine Methoxy- oder eine Ethoxygruppe. Weiterhin können als bevorzugte Beispiele für eine C bis C -Hydroxyalkylgruppe eine Hydroxymethyi-, eine 2-Hydroxyethyl-, eine 3-Hydroxypropyl- oder eine 4-Hydroxybutylgruppe genannt werden. Eine 2-Hydroxyethylgruppe ist besonders bevorzugt. Eine besonders bevorzugte C2- bis C4-Polyhydroxyalkylgruppe ist die 1 ,2-Dihydroxyethylgruppe. Beispiele für Halogenatome sind erfindungsgemäß F-, Cl- oder Br-Atome, Cl-Atome sind ganz besonders bevorzugt. Die weiteren verwendeten Begriffe leiten sich erfindungsgemäß von den hier gegebenen Definitionen ab. Beispiele für stickstoffhaltige Gruppen der Formel (E1) sind insbesondere die Aminogruppen, Cr bis C4-Monoalkylaminogruppen, d- bis C4-Dialkylaminogruppen, C bis C4-Trialkylammoniumgruppen, C bis C - Monohydroxyalkylaminogruppen, Imidazolinium und Ammonium.Examples of the Cr to C alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Cr to C 4 alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C to C -hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C 2 - to C 4 -polyhydroxyalkyl group is the 1, 2-dihydroxyethyl. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, Cr to C 4 -monoalkylamino groups, d- to C 4 -dialkylamino groups, C to C 4 -trialkylammonium groups, C to C-monohydroxyalkylamino groups, imidazolinium and ammonium.
Besonders bevorzugte p-Phenylendiamine der Formel (E1) sind ausgewählt aus p- Phenylendiamin, p-Toluylendiamin, 2-Chlor-p-phenylendiamin, 2,3-Dimethyl-p- phenylendiamin, 2,6-Dimethyl-p-phenylendiamin, 2,6-Diethyl-p-phenylendiamin, 2,5- Dimethyl-p-phenylendiamin, N,N-Dimethyl-p-phenylendiamin, N,N-Diethyl-p-phenylen- diamin, N,N-Dipropyl-p-phenylendiamin, 4-Amino-3-methyl-(N,N-diethyl)-anilin, N,N-Bis- (ß-hydroxyethyl)-p-phenylendiamin, 4-N,N-Bis-(ß-hydroxyethyl)-amino-2-methylanilin, 4- N,N-Bis-(ß-hydroxyethyl)-amino-2-chloranilin, 2-(ß-Hydroxyethyl)-p-phenylendiamin, 2- (α,ß-Dihydroxyethyl)-p-phenylendiamin, 2-Fluor-p-phenylendiamin, 2-lsopropyl-p- phenylendiamin, N-(ß-Hydroxypropyl)-p-phenylendiamin, 2-Hydroxymethyl-p- phenylendiamin, N,N-Dimethyl-3-methyl-p-phenylendiamin, N,N-(Ethyl,ß-hydroxyethyl)-p- phenylendiamin, N-(ß,γ-Dihydroxypropyl)-p-phenylendiamin, N-(4'-Aminophenyl)-p- phenylendiamin, N-Phenyl-p-phenylendiamin, 2-(ß-Hydroxyethyloxy)-p-phenylendiamin, 2- (ß-Acetylaminoethyloxy)-p-phenylendiamin, N-(ß-Methoxyethyl)-p-phenylendiamin und 5,8-Diaminobenzo-1,4-dioxan sowie ihren physiologisch verträglichen Salzen.Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine , 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (ß-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (ß-hydroxyethyl) amino -2-methylaniline, 4- N, N-bis (ß-hydroxyethyl) amino-2-chloroaniline, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p- phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl , ß-hydroxyethyl) -p-phenylenediamine, N- (ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß- Hydroxyethyloxy) -p-phenylenediamine, 2- (ß-acetylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.
Erfindungsgemäß ganz besonders bevorzugte p-Phenylendiaminderivate der Formel (E1) sind p-Phenylendiamin, p-Toluylendiamin, 2-(ß-Hydroxyethyl)-p-phenylendiamin, 2-(α,ß- Dihydroxyethyl)-p-phenylendiamin und N,N-Bis-(ß-hydroxyethyl)-p-phenylendiamin.According to the invention, p-phenylenediamine derivatives of the formula (E1) which are particularly preferred are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.
Es kann erfindungsgemäß weiterhin bevorzugt sein, als Entwicklerkomponente Verbindungen einzusetzen, die mindestens zwei aromatische Kerne enthalten, die mit Amino- und/oder Hydroxylgruppen substituiert sind.It can also be preferred according to the invention to use, as developer component, compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.
Unter den zweikernigen Entwicklerkomponenten, die in den Färbezusammensetzungen gemäß der Erfindung verwendet werden können, kann man insbesondere die Verbindungen nennen, die der folgenden Formel (E2) entsprechen, sowie ihre physiologisch verträglichen Salze:Among the binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:
Figure imgf000006_0001
wobei:
Figure imgf000006_0001
in which:
- Z1 und Z2 stehen unabhängig voneinander für einen Hydroxyl- oder NH2-Rest, der gegebenenfalls durch einen C bis C4-Alkylrest, durch einen C bis C4-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist, - die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Hetero- atomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder d- bis C8-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,Z 1 and Z 2 independently of one another represent a hydroxyl or NH 2 radical which is optionally substituted by a C to C 4 alkyl radical, by a C to C 4 hydroxyalkyl radical and / or by a bridging Y or which is optionally Is part of a bridging ring system, - The bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is interrupted by one or more nitrogen-containing groups and / or one or more hetero atoms such as oxygen, sulfur or nitrogen atoms or may be terminated and may be substituted by one or more hydroxyl or d to C 8 alkoxy radicals, or a direct bond,
- G5 und G6 stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen d- bis C4-Alkylrest, einen d- bis C -Monohydroxyalkylrest, einen C2- bis C4- Polyhydroxyalkylrest, einen C bis C4-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,- G 5 and G 6 are each independently a hydrogen or halogen atom, a d- to C 4 alkyl, a d- to C monohydroxyalkyl radical, a C 2 - to C 4 - polyhydroxyalkyl radical, a C to C 4 -aminoalkyl or a direct connection to bridge Y,
- G7, G8, G9, G10, G11 und G12 stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen d- bis C -Alkylrest, mit den Maßgaben, dass- G 7 , G 8 , G 9 , G 10 , G 11 and G 12 independently of one another represent a hydrogen atom, a direct bond to the bridging Y or a d- to C -alkyl radical, with the provisos that
- die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.- The compounds of formula (E2) contain only one bridge Y per molecule and the compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.
Die in Formel (E2) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.According to the invention, the substituents used in formula (E2) are defined analogously to the above statements.
Bevorzugte zweikernige Entwicklerkomponenten der Formel (E2) sind insbesondere: N,N'-Bis-(ß-hydroxyethyl)-N,N,-bis-(4'-aminophenyl)-1 ,3-diamino-propan-2-ol, N,N'-Bis-(ß- hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-ethylendiamin, N,N'-Bis-(4-aminophenyl)- tetramethylendiamin, N,N'-Bis-(ß-hydroxyethyl)-N,N'-bis-(4-aminophenyl)-tetramethylen- diamin, N,N'-Bis-(4-methyl-aminophenyl)-tetramethylendiamin, N,N'-Diethyl-N,N,-bis-(4'- amino-3'-methylphenyl)-ethylendiamin, Bis-(2-hydroxy-5-aminophenyl)-methan, 1 ,3-Bis- (2,5-diaminophenoxy)-propan-2-ol, N,N'-Bis-(4'-aminophenyl)-1 ,4-diazacycloheptan, N,N'- Bis-(2-hydroxy-5-aminobenzyl)-piperazin, N-(4'-Aminophenyl)-p-phenylendiamin und 1 ,10- Bis-(2',5'-diaminophenyl)-1 ,4,7,10-tetraoxadecan und ihre physiologisch verträglichen Salze.Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis- (β-hydroxyethyl) -N, N , -bis- (4'-aminophenyl) -1, 3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis - (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) -tetramethylene-diamine, N, N'-bis- (4-methyl-aminophenyl) -tetramethylene-diamine, N, N'-diethyl-N, N , -bis- (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) propane-2 -ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10- bis- (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane and their physiologically tolerable salts.
Besonders bevorzugte zweikernige Entwicklerkomponenten der Formel (E2) sind N,N'- Bis-(ß-hydroxyethyl)-N,N,-bis-(4'-aminophenyl)-1 ,3-diamino-propan-2-ol, Bis-(2-hydroxy-5- aminophenyl)-methan, 1 ,3-Bis-(2,5-diaminophenoxy)-propan-2-ol, N,N'-Bis-(4'-amino- phenyl)-1 ,4-diazacycloheptan und 1 ,10-Bis-(2',5'-diaminophenyl)-1 ,4,7,10-tetraoxadecan oder eines ihrer physiologisch verträglichen Salze. Bis-(2-hydroxy-5-aminophenyl)-methan ist eine ganz besonders bevorzugte zweikernige Entwicklerkomponente der Formel (E2).Particularly preferred dinuclear developer components of the formula (E2) are N, N'-bis (ß-hydroxyethyl) -N, N , -bis- (4'-aminophenyl) -1, 3-diamino-propan-2-ol, bis - (2-Hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4'-aminophenyl) -1 , 4-diazacycloheptane and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of their physiologically tolerable salts. Bis- (2-hydroxy-5-aminophenyl) methane is a very particularly preferred dinuclear developer component of the formula (E2).
Weiterhin kann es erfindungsgemäß bevorzugt sein, als Entwicklerkomponente ein p- Aminophenolderivat oder eines seiner physiologisch verträglichen Salze einzusetzen. Besonders bevorzugt sind p-Aminophenolderivate der Formel (E3)Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (E3) are particularly preferred
Figure imgf000008_0001
Figure imgf000008_0001
wobei:in which:
- G13 steht für ein Wasserstoffatom, ein Halogenatom, einen d- bis C4-Alkylrest, einen d- bis C4-Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (Cr bis C4)- Alkoxy-(d- bis C4)-alkylrest, einen d- bis C -Aminoalkylrest, einen Hydroxy-(C bis C4)- alkylaminorest, einen Cr bis C4-Hydroxyalkoxyrest, einen d- bis C4-Hydroxyalkyl-(d-bis C4)-aminoalkylrest oder einen (Di-Cr bis C4-Alkylamino)-(C bis C4)-alkylrest, und- G 13 represents a hydrogen atom, a halogen atom, ad- to C 4 -alkyl residue, ad- to C 4 -monohydroxyalkyl residue, a C 2 - to C 4 -polyhydroxyalkyl residue, a (Cr to C 4 ) - alkoxy- ( d- to C 4 ) -alkyl radical, a d- to C -aminoalkyl radical, a hydroxy- (C to C 4 ) -alkylamino radical, a Cr to C 4 -hydroxyalkoxy radical, ad- to C 4 -hydroxyalkyl- (d-bis C 4 ) aminoalkyl or a (di-C r to C 4 alkylamino) - (C to C 4 ) alkyl, and
- G14 steht für ein Wasserstoff- oder Halogenatom, einen Cr bis C -Alkylrest, einen d- bis C4-Monohydroxyalkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen (d- bis C4)- Alkoxy-(d- bis C4)-alkylrest, einen Cr bis C4-Aminoalkylrest oder einen C bis C4- Cyanoalkylrest,- G 14 represents a hydrogen or halogen atom, a Cr to C alkyl group, a d to C 4 monohydroxyalkyl group, a C 2 to C 4 polyhydroxyalkyl group, a (d to C 4 ) alkoxy (i.e. - to C 4 ) -alkyl radical, a C r to C 4 -aminoalkyl radical or a C to C 4 -cyanoalkyl radical,
- G15 steht für Wasserstoff, einen Cr bis C -Alkylrest, einen C bis C4-Monohydroxy- alkylrest, einen C2- bis C4-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und- G 15 represents hydrogen, a C r to C alkyl radical, a C to C 4 monohydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
- G16 steht für Wasserstoff oder ein Halogenatom.- G 16 represents hydrogen or a halogen atom.
Die in Formel (E3) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.According to the invention, the substituents used in formula (E3) are defined analogously to the above statements.
Bevorzugte p-AminophenoIe der Formel (E3) sind insbesondere p-Aminophenol, N- Methyl-p-aminophenol, 4-Amino-3-methyl-phenol, 4-Amino-3-fluorphenol, 2- Hydroxymethylamino-4-aminophenol, 4-Amino-3-hydroxymethylphenol, 4-Amino-2-(ß- hydroxyethoxy)-phenol, 4-Amino-2-methylphenol, 4-Amino-2-hydroxymethylphenol, 4- Amino-2-methoxymethyl-phenol, 4-Amino-2-aminomethylphenol, 4-Amino-2-(ß- hydroxyethyl-aminomethyl)-phenol, 4-Amino-2-(α,ß-dihydroxyethyl)-phenol, 4-Amino-2- fluorphenol, 4-Amino-2-chlorphenol, 4-Amino-2,6-dichlorphenol, 4-Amino-2-(diethyl- aminomethyl)-phenol sowie ihre physiologisch verträglichen Salze.Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2- Hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (ß-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2- methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, ß-dihydroxyethyl) phenol, 4-amino-2- fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically tolerable salts.
Ganz besonders bevorzugte Verbindungen der Formel (E3) sind p-Aminophenol, 4- Amino-3-methylphenol, 4-Amino-2-aminomethylphenol, 4-Amino-2-(α,ß-dihydroxyethyl)- phenol und 4-Amino-2-(diethyl-aminomethyl)-phenol.Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino- 2- (diethylaminomethyl) -phenol.
Ferner kann die Entwicklerkomponente ausgewählt sein aus o-Aminophenol und seinen Derivaten, wie beispielsweise 2-Amino-4-methylphenol, 2-Amino-5-methylphenol oder 2- Amino-4-chlorphenol.Furthermore, the developer component can be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.
Weiterhin kann die Entwicklerkomponente ausgewählt sein aus heterocyclischen Entwicklerkomponenten, wie beispielsweise den Pyridin-, Pyrimidin-, Pyrazol-, Pyrazol- Pyrimidin-Derivaten und ihren physiologisch verträglichen Salzen.Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.
Bevorzugte Pyridin-Derivate sind insbesondere die Verbindungen, die in den Patenten GB 1 026 978 und GB 1 153 196 beschrieben werden, wie 2,5-Diamino-pyridin, 2-(4'- Methoxyphenyl)-amino-3-amino-pyridin, 2,3-Diamino-6-methoxy-pyridin, 2-(ß-Preferred pyridine derivatives are, in particular, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine , 2,3-diamino-6-methoxy-pyridine, 2- (ß-
MethoxyethyI)-amino-3-amino-6-methoxy-pyridin und 3,4-Diamino-pyridin.MethoxyethyI) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.
Bevorzugte Pyrimidin-Derivate sind insbesondere die Verbindungen, die im deutschen Patent DE 2 359 399, der japanischen Offenlegungsschrift JP 02019576 A2 oder in der Offenlegungsschrift WO 96/15765 beschrieben werden, wie 2,4,5,6-Tetraaminopyrimidin, 4-Hydroxy-2,5,6-triaminopyrimidin, 2-Hydroxy-4,5,6-triaminopyrimidin, 2-Dimethylamino- 4,5,6-triaminopyrimidin, 2,4-Dihydroxy-5,6-diaminopyrimidin und 2,5,6-Triaminopyrimidin.Preferred pyrimidine derivatives are, in particular, the compounds which are described in German patent DE 2 359 399, Japanese laid-open patent publication JP 02019576 A2 or in laid-open publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- triaminopyrimidine.
Bevorzugte Pyrazol-Derivate sind insbesondere die Verbindungen, die in den Patenten DE 3 843 892, DE 4 133 957 und Patentanmeldungen WO 94/08969, WO 94/08970, EP- 740 931 und DE 195 43 988 beschrieben werden, wie 4,5-Diamino-1-methylpyrazol, 4,5- Diamino-1 -(ß-hydroxyethyl)-pyrazol, 3,4-Diaminopyrazol, 4,5-Diamino-1 -(4'-chlorbenzyl)- pyrazol, 4,5-Diamino-1 ,3-dimethylpyrazol, 4,5-Diamino-3-methyl-1-phenylpyrazol, 4,5- Diamino-1-methyl-3-phenylpyrazol, 4-Amino-1 ,3-dimethyl-5-hydrazinopyrazol, 1-Benzyl- 4,5-diamino-3-methylpyrazol, 4,5-Diamino-3-tert.-butyl-1-methylpyrazol, 4,5-Diamino-1- tert.-butyl-3-methylpyrazol, 4,5-Diamino-1 -(ß-hydroxyethyl)-3-methylpyrazol, 4,5-Diamino- 1-ethyl-3-methylpyrazol, 4,5-Diamino-1-ethyl-3-(4'-methoxyphenyl)-pyrazol, 4,5-Diamino- 1 -ethyl-3-hydroxymethylpyrazol, 4,5-Diamino-3-hydroxymethyl-1 -methylpyrazol, 4,5- Diamino-3-hydroxymethyl-1 -isopropylpyrazol, 4,5-Diamino-3-methyl-1 -isopropylpyrazol, 4- Amino-5-(ß-aminoethyl)-amino-1 ,3-di methylpyrazol, 3,4,5-Triaminopyrazol, 1-Methyl- 3,4,5-triaminopyrazol, 3,5-Diamino-1-methyl-4-methylaminopyrazol und 3,5-Diamino-4-(ß- hydroxyethyl)-amino-1 -methylpyrazol.Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4.5 -Diamino-1-methylpyrazole, 4,5- diamino-1 - (ß-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 - (4'-chlorobenzyl) - pyrazole, 4,5- Diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5- Diamino-1-methyl-3-phenylpyrazole, 4-amino-1, 3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl -1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1 - (ß-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl- 3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1 -methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (ß-aminoethyl) -amino-1, 3-di methylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (ß-hydroxyethyl) - amino-1-methylpyrazole.
Bevorzugte Pyrazol-Pyrimidin-Derivate sind insbesondere die Derivate des Pyrazol-[1 ,5- a]-pyrimidin der folgenden Formel (E4) und dessen tautomeren Formen, sofern ein tauto- meres Gleichgewicht besteht:Preferred pyrazole-pyrimidine derivatives are in particular the derivatives of pyrazole- [1,5-a] -pyrimidine of the following formula (E4) and its tautomeric forms, provided there is a tautomeric equilibrium:
Figure imgf000010_0001
wobei:
Figure imgf000010_0001
in which:
- G17, G18, G19 und G20 unabhängig voneinander stehen für ein Wasserstoffatom, einen Cr bis C4-Alkylrest, einen Aryl-Rest, einen C bis C -Hydroxyalkylrest, einen C2- bis C - Polyhydroxyalkylrest einen (C bis C4)-Alkoxy-(Cr bis C4)-alkylrest, einen C bis C4- Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C bis C )-Alkylamino-(d- bis C )-alkylrest, einen Di-[(d- bis C4)-alkyl]-(Cr bis C4)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen d- bis C4-Hydroxyalkyl- oder einen Di-(d- bis C4)-[Hydroxyalkyl]-(C bis C4)-aminoalkylrest,- G 17 , G 18 , G 19 and G 20 independently represent a hydrogen atom, a Cr to C 4 alkyl radical, an aryl radical, a C to C hydroxyalkyl radical, a C 2 to C polyhydroxyalkyl radical a (C to C 4 ) -alkoxy- (Cr to C 4 ) -alkyl, a C to C 4 -aminoalkyl radical, which can optionally be protected by an acetyl-ureide or a sulfonyl radical, a (C to C) -alkylamino- (d- to C) -alkyl radical, a di - [(d- to C 4 ) -alkyl] - (Cr to C 4 ) -aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links , ad- to C 4 -hydroxyalkyl or di- (d- to C 4 ) - [hydroxyalkyl] - (C to C 4 ) aminoalkyl,
- die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C bis C4- Alkylrest, einen Aryl-Rest, einen d- bis C4-Hydroxyalkylrest, einen C2- bis C4- Polyhydroxyalkylrest, einen C bis C4-Aminoalkylrest, einen (C bis C4)-Alkylamino-(d- bis C4)-alkylrest, einen Di-[(C bis C )alkyl]- (d- bis C )-aminoalkylrest, wobei die Dialkyl- Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C bis C4-Hydroxyalkyl- oder einen Di-(C bis C4-hydroxy- alkyl)-aminoalkylrest, einen Aminorest, einen d- bis C4-Alkyl- oder Di-(d- bis C4-hydroxy- alkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäure- gruppe, i hat den Wert 0, 1 , 2 oder 3, p hat den Wert 0 oder 1 , q hat den Wert 0 oder 1 und n hat den Wert 0 oder 1 , mit der Maßgabe, dass die Summe aus p + q ungleich 0 ist, wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG17G18 und NG19G20 belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7); wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG17G18 (oder NG19G20) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);- The X radicals independently of one another represent a hydrogen atom, a C to C 4 alkyl radical, an aryl radical, a d to C 4 hydroxyalkyl radical, a C 2 to C 4 polyhydroxyalkyl radical, a C to C 4 Aminoalkyl radical, a (C to C 4 ) alkylamino (d to C 4 ) alkyl radical, a di - [(C to C) alkyl] - (d to C) aminoalkyl radical, the dialkyl radicals optionally having one Form carbon cycle or a heterocycle with 5 or 6 chain links, a C to C 4 hydroxyalkyl or a di (C to C 4 hydroxyalkyl) aminoalkyl radical, an amino radical, a d to C 4 alkyl or di - (d- to C 4 -hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0 when p + q is 2, n is 0 and the groups NG 17 G 18 and NG 19 G 20 occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7); if p + q is 1, n is 1, and the groups NG 17 G 18 (or NG 19 G 20 ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);
Die in Formel (E4) verwendeten Substituenten sind erfindungsgemäß analog zu den obigen Ausführungen definiert.According to the invention, the substituents used in formula (E4) are defined analogously to the above statements.
Wenn das Pyrazol-[1,5-a]-pyrimidin der obenstehenden Formel (E4) eine Hydroxygruppe an einer der Positionen 2, 5 oder 7 des Ringsystems enthält, besteht ein tautomeres Gleichgewicht, das zum Beispiel im folgenden Schema dargestellt wird:If the pyrazole [1,5-a] pyrimidine of the formula (E4) above contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, for example, in the following scheme:
Figure imgf000011_0001
Figure imgf000011_0001
Unter den Pyrazol-[1 ,5-a]-pyrimidinen der obenstehenden Formel (E4) kann man insbesondere nennen: Pyrazol-[1 ,5-a]-pyrimidin-3,7-diamin; 2,5-Dimethyl-pyrazol-[1 ,5-a]-pyrimidin-3,7-diamin; Pyrazol-[1 ,5-a]-pyrimidin-3,5-diamin; 2,7-Dimethyl-pyrazol-[1 ,5-a]-pyrimidin-3,5-diamin; 3-Aminopyrazol-[1 ,5-a]-pyrimidin-7-ol; 3-Aminopyrazol-[1 ,5-a]-pyrimidin-5-ol; 2-(3-Aminopyrazol-[1 ,5-a]-pyrimidin-7-ylamino)-ethanol; 2-(7-Aminopyrazol-[1 ,5-a]-pyrimidin-3-ylamino)-ethanol; 2-[(3-Aminopyrazol-[1 ,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol; 2-[(7-Aminopyrazol-[1 ,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol; 5,6-DimethylpyrazoI-[1 ,5-a]-pyrimidin-3,7-diamin; 2,6-Dimethylpyrazol-[1 ,5-a]-pyrimidin-3,7-diamin; 3-Amino-7-dimethylamino-2,5-dimethylpyrazol-[1 ,5-a]-pyrimidin; sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.Among the pyrazole- [1, 5-a] pyrimidines of the above formula (E4) one can mention in particular: pyrazole- [1, 5-a] pyrimidine-3,7-diamine; 2,5-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine; Pyrazole- [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethylpyrazole- [1,5-a] pyrimidine-3,5-diamine; 3-aminopyrazole- [1,5-a] pyrimidin-7-ol; 3-aminopyrazole- [1,5-a] pyrimidin-5-ol; 2- (3-aminopyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol; 2- (7-aminopyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-aminopyrazole- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(7-aminopyrazole- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol; 5,6-dimethylpyrazoI- [1,5-a] pyrimidine-3,7-diamine; 2,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine; 3-amino-7-dimethylamino-2,5-dimethylpyrazole- [1,5-a] pyrimidine; as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.
Die Pyrazol-[1 ,5-a]-pyrimidine der obenstehenden Formel (E4) können wie in der Literatur beschrieben durch Zyklisierung ausgehend von einem Aminopyrazol oder von Hydrazin hergestellt werden.The pyrazole [1, 5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.
In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Zweikomponentenmittels enthält die Zubereitung (A) mindestens eine Kupplerkomponente.In a further preferred embodiment of the two-component agent according to the invention, preparation (A) contains at least one coupler component.
Als Kupplerkomponenten werden in der Regel m-Phenylendiaminderivate, Naphthole, Re- sorcin und Resorcinderivate, Pyrazolone und m-Aminophenolderivate verwendet. Als Kupplersubstanzen eignen sich insbesondere 1-Naphthol, 1 ,5-, 2,7- und 1 ,7-Dihydroxy- naphthalin, 5-Amino-2-methylphenol, m-Aminophenol, Resorcin, Resorcinmonomethyl- ether, m-Phenylendiamin, 1-Phenyl-3-methyl-pyrazolon-5, 2,4-Dichlor-3-aminophenol, 1 ,3-Bis-(2',4'-diaminophenoxy)-propan, 2-Chlor-resorcin, 4-Chlor-resorcin, 2-Chlor-6- methyl-3-aminophenol, 2-Amino-3-hydroxypyridin, 2-Methylresorcin, 5-Methylresorcin und 2-Methyl-4-chlor-5-aminophenol.M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components. Suitable coupler substances are in particular 1-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxy-naphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1 -Phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol , 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.
Erfindungsgemäß bevorzugte Kupplerkomponenten sind m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N- Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4- aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6- methylphenol, 5-Amino-4-chlor-2-methylphenol, 5-Amino-4-methoxy-2-methyiphenol, 5-(2'-Hydroxyethyl)-amino-2-methylphenol, 3-(Diethylamino)-phenol, N-Cyclopentyl-3- aminophenol, 1 ,3-Dihydroxy-5-(methylamino)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol, o-Aminophenol und dessen Derivate, m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4- Diaminophenoxyethanol, 1 ,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino- 4-(2'-hydroxyethylamino)benzol, 1 ,3-Bis-(2',4,-diaminophenyl)-propan, 2,6-Bis-(2'- hydroxyethylamino)-1 -methylbenzol und 1 -Amino-3-bis-(2'-hydroxyethyl)-aminobenzol, - o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,Coupler components preferred according to the invention are m-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2, 6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methyiphenol, 5- (2'- Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4 -Dichlor-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, 1-methoxy- 2-amino- 4- (2'-hydroxyethylamino) benzene, 1, 3-bis- (2 ', 4 , -diaminophenyl) propane, 2,6-bis- (2'-hydroxyethylamino) -1-methylbenzene and 1 amino-3-bis- (2'-hydroxyethyl) aminobenzene, o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene,
- Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
- Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2- Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6- Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3- Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin, Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1 ,5-Dihydroxynaphthalin, 1,6- Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1 ,8-Dihydroxynaphthalin, 2,7- Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin, Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Amino- benzomorpholin, Chinoxalinderivate wie beispielsweise 6-Methyl-1 ,2,3,4-tetrahydrochinoxalin, Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on, Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol, Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6- dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2- Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2- methylpyrimidin, oder Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1 -Amino-3,4-methylendioxybenzol und 1 -(2'-Hydroxyethyl)-amino-3,4- methylendioxybenzol.Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2 -Methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2.7 - Dihydroxynaphthalene and 2,3-dihydroxynaphthalene, morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine, quinoxaline derivatives such as 6-methyl-1, 2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazole - 5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxyp yrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1 - (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.
Erfindungsgemäß besonders bevorzugte Kupplerkomponenten sind 1-Naphthol, 1,5-, 2,7- und 1,7-Dihydroxynaphthalin, 3-Aminophenol, 5-Amino-2-methylphenol, 2-Amino-3- hydroxypyridin, Resorcin, 4-Chlorresorcin, 2-Chlor-6-methyl-3-aminophenol, 2-Methyl- resorcin, 5-Methylresorcin, 2,5-Dimethylresorcin und 2,6-Dihydroxy-3,4-dimethylpyridin.Coupler components which are particularly preferred according to the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.
Im Rahmen der vorliegenden Erfindung kann es besonders bevorzugt sein, wenn die Zubereitung (A) mindestens eine Entwicklerkomponente, ausgewählt aus p-Phenylen- diamin, p-Toluylendiamin, p-Aminophenol, N,N-Bis-(2-hydroxyethyl)-p-phenylendiamin, 1- (2-Hydroxyethyl)-2,5-diaminobenzol, 3-Methyl-4-aminophenol, Bis-(2-hydroxy-5-amino- phenyl)methan, 2,4,5, 6-Tetraaminopyrimidin und 1-(2-Hydroxyethyl)-4,5-diaminopyrazol, und/oder mindestens eine weitere Kupplerkomponente, ausgewählt aus 2-(2,4-Diamino- phenoxy)ethanol, 1 ,3-Bis-(2,4-diaminophenoxy)-propan, 5-Amino-2-methylphenol, 2- Amino-3-hydroxypyridin, Resorcin, 2-Methylresorcin, 4-Chlorresorcin, 2-Amino-4-(2- hydroxyethylamino)anisol, 2,7-Dihydroxynaphthalin und 3-Aminophenol, enthält.In the context of the present invention, it can be particularly preferred if the preparation (A) has at least one developer component selected from p-phenylenediamine, p-toluenediamine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p -phenylenediamine, 1- (2-hydroxyethyl) -2,5-diaminobenzene, 3-methyl-4-aminophenol, bis- (2-hydroxy-5-amino- phenyl) methane, 2,4,5, 6-tetraaminopyrimidine and 1- (2-hydroxyethyl) -4,5-diaminopyrazole, and / or at least one further coupler component selected from 2- (2,4-diaminophenoxy) ethanol , 1,3-bis- (2,4-diaminophenoxy) propane, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 2-amino-4- ( 2-hydroxyethylamino) anisole, 2,7-dihydroxynaphthalene and 3-aminophenol.
Die Entwicklerkomponenten und die Kupplerkomponenten sind in der Zubereitung (A) bevorzugt in einer Menge von 0,005 bis 20 Gew.-%, vorzugsweise 0,1 bis 5 Gew.-%, enthalten, jeweils bezogen auf das gesamte Zweikomponentenmittel. Dabei werden Entwicklerkomponenten und Kupplerkomponenten im allgemeinen in etwa molaren Mengen zueinander eingesetzt. Wenn sich auch der molare Einsatz als zweckmäßig erwiesen hat, so ist ein gewisser Uberschuss einzelner Oxidationsfarbstoffvorprodukte nicht nachteilig, so dass Entwicklerkomponenten und Kupplerkomponenten in einem Mol- Verhältnis von 1 :0,5 bis 1:3, insbesondere 1 :1 bis 1:2, enthalten sein können.The developer components and the coupler components are preferably present in preparation (A) in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, in each case based on the total two-component agent. Developer components and coupler components are generally used in approximately molar amounts to one another. If molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can be included.
Weiterhin kann die Zubereitung (A) erfindungsgemäß eine Vorstufe eines naturanalogen Farbstoffs enthalten. Als Vorstufen naturanaloger Farbstoffe werden bevorzugt solche lndole und Indoline eingesetzt, die mindestens eine Hydroxy- oder Aminogruppe, bevorzugt als Substituent am Sechsring, aufweisen. Diese Gruppen können weitere Substituenten tragen, z. B. in Form einer Veretherung oder Veresterung der Hydroxygruppe oder eine Alkylierung der Aminogruppe. In einer zweiten bevorzugten Ausführungsform enthalten die Färbemittel mindestens ein Indol- und/oder Indolinderivat.Preparation (A) according to the invention can furthermore contain a precursor of a nature-analogous dye. Those indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.
Besonders gut als Vorstufen naturanaloger Haarfarbstoffe geeignet sind Derivate des 5,6- Dihydroxyindolins der Formel (la),Derivatives of 5,6-dihydroxyindoline of the formula (Ia) are particularly suitable as precursors of naturally analogous hair dyes,
Figure imgf000014_0001
(la) R K1 in der unabhängig voneinander
Figure imgf000014_0001
(la) RK 1 in the independently of each other
- R1 steht für Wasserstoff, eine d-C4-Alkylgruppe oder eine d-C4-Hydroxy-alkylgruppe,R 1 represents hydrogen, a dC 4 -alkyl group or a dC 4 -hydroxy-alkyl group,
- R2 steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,R 2 stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
- R3 steht für Wasserstoff oder eine d-C -Alkylgruppe, - R4 steht für Wasserstoff, eine d-C -Alkylgruppe oder eine Gruppe -CO-R6, in der R6 steht für eine CrC -Alkylgruppe, undR 3 represents hydrogen or a dC -alkyl group, - R 4 stands for hydrogen, a dC -alkyl group or a group -CO-R 6 , in which R 6 stands for a CrC -alkyl group, and
- R5 steht für eine der unter R4 genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.- R 5 stands for one of the groups mentioned under R 4 , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.
Besonders bevorzugte Derivate des Indolins sind das 5,6-Dihydroxyindolin, N-Methyl-5,6- dihydroxyindolin, N-Ethyl-5,6-dihydroxyindolin, N-Propyl-5,6-dihydroxyindolin,Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline,
N-Butyl-5,6-dihydroxyindolin, 5,6-Dihydroxyindolin-2-carbonsäure sowie das 6-Hydroxy- indolin, das 6-Aminoindolin und das 4-Aminoindolin.N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and the 6-hydroxyindoline, the 6-aminoindoline and the 4-aminoindoline.
Besonders hervorzuheben sind innerhalb dieser Gruppe N-Methyl-5,6-dihydroxyindolin, N-Ethyl-5,6-dihydroxyindolin, N-Propyl-5,6-dihydroxyindolin, N-Butyl-5,6-dihydroxyindolin und insbesondere das 5,6-Dihydroxyindolin.Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially the 5 6-Dihydroxyindolin.
Als Vorstufen naturanaloger Haarfarbstoffe hervorragend geeignet sind weiterhin Derivate des 5,6-Dihydroxyindols der Formel (Ib),Derivatives of 5,6-dihydroxyindole of the formula (Ib) are also outstandingly suitable as precursors of nature-analogous hair dyes,
Figure imgf000015_0001
Figure imgf000015_0001
in der unabhängig voneinanderin the independently of each other
- R1 steht für Wasserstoff, eine C C4-Alkylgruppe oder eine d-C4-Hydroxyalkylgruppe, R2 steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann, R3 steht für Wasserstoff oder eine d-C4-Alkylgruppe, R4 steht für Wasserstoff, eine d-d-Alkylgruppe oder eine Gruppe -CO-R6, in der R6 steht für eine CrC4-Alkylgruppe, und R5 steht für eine der unter R4 genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure. Besonders bevorzugte Derivate des Indols sind 5,6-Dihydroxyindol, N-Methyl-5,6-dihy- droxyindol, N-Ethyl-5,6-dihydroxyindol, N-Propyl-5,6-dihydroxyindol, N-Butyl-5,6-dihy- droxyindol, 5,6-Dihydroxyindol-2-carbonsäure, 6-Hydroxyindol, 6-Aminoindol und 4- Aminoindol.R 1 stands for hydrogen, a CC 4 -alkyl group or a dC 4 -hydroxyalkyl group, R 2 stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation, R 3 stands for hydrogen or a dC 4 -alkyl group, R 4 stands for hydrogen, a dd-alkyl group or a group -CO-R 6 , in which R 6 stands for a CrC 4 -alkyl group, and R 5 stands for one of those under R. 4 mentioned groups, as well as physiologically tolerable salts of these compounds with an organic or inorganic acid. Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
Innerhalb dieser Gruppe hervorzuheben sind N-Methyl-5,6-dihydroxyindol, N-Ethyl-5,6- dihydroxyindol, N-Propyl-5,6-dihydroxyindol, N-Butyl-5,6-dihydroxyindol sowie insbesondere das 5,6-Dihydroxyindol.Within this group, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 are to be emphasized -Dihydroxyindol.
Die Indolin- und Indol-Derivate können in den erfindungsgemäßen Zweikomponentenmitteln sowohl als freie Basen als auch in Form ihrer physiologisch verträglichen Salze mit anorganischen oder organischen Säuren, z. B. der Hydrochloride, der Sulfate und Hydro- bromide, eingesetzt werden. Die Indol- oder Indolin-Derivate sind in diesen üblicherweise in Mengen von 0,05-10 Gew.-%, vorzugsweise 0,2-5 Gew.-%, jeweils bezogen auf das gesamte Zweikomponentenmittel, enthalten.The indoline and indole derivatives can be in the two-component compositions according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochlorides, sulfates and hydrobromides can be used. The indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight, based in each case on the total two-component agent.
In einer weiteren Ausführungsform kann es erfindungsgemäß bevorzugt sein, das Indolin- oder Indolderivat in Haarfärbemitteln in Kombination mit mindestens einer Aminosäure oder einem Oligopeptid einzusetzen. Die Aminosäure ist vorteilhafterweise eine α-Ami- nosäure; ganz besonders bevorzugte α-Aminosäuren sind Arginin, Ornithin, Lysin, Serin und Histidin, insbesondere Arginin.In a further embodiment it can be preferred according to the invention to use the indoline or indole derivative in hair colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.
Neben den Entwicklerkomponenten und/oder den Kupplerkomponenten kann die Zubereitung (A) erfindungsgemäß zur Nuancierung einen oder mehrere direktziehende Farbstoffe enthalten. Direktziehende Farbstoffe sind üblicherweise Nitrophenylendiamine, Nitroaminophenole, Azofarbstoffe, Anthrachinone oder Indophenole. Bevorzugte direktziehende Farbstoffe sind die unter den internationalen Bezeichnungen bzw. Handelsnamen HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1 , Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1 , HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57:1, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1 , Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, und Acid Black 52 bekannten Verbindungen sowie 1 ,4-Diamino-2-nitrobenzol, 2-Amino-4-nitrophenol, 1 ,4-Bis-(ß- hyd roxyethyl)-amino-2-nitrobenzol, 3-Nitro-4-(ß-hydroxyethyl)-aminophenol, 2-(2'- Hydroxyethyl)amino-4,6-dinitrophenol, 1-(2'-Hydroxyethyl)amino-4-methyl-2-nitrobenzol, 1-Amino-4-(2'-hydroxyethyl)-amino-5-chlor-2-nitrobenzol, 4-Amino-3-nitrophenol, 1-(2'- Ureidoethyl)amino-4-nitrobenzol, 4-Amino-2-nitrodiphenylamin-2'-carbonsäure, 6-Nitro- 1 ,2,3,4-tetrahydrochinoxalin, 2-Hydroxy-1,4-naphthochinon, Pikraminsäure und deren Salze, 2-Amino-6-chloro-4-nitrophenol, 4-Ethylamino-3-nitrobenzoesäure und 2-Chloro-6- ethylamino-1-hydroxy-4-nitrobenzol.In addition to the developer components and / or the coupler components, the preparation (A) according to the invention can contain one or more substantive dyes for shading. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds and 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis (ß-hydoxyethyl) -amino-2-nitrobenzene, 3-nitro-4- (ß-hydroxyethyl ) -aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2 -nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4 -Ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung enthält die Zubereitung (A) einen kationischen direktziehenden Farbstoff. Besonders bevorzugt sind dabei (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14, (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie (c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.In a preferred embodiment of the present invention, preparation (A) contains a cationic direct dye. Particular preference is given to (a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, (b) aromatic systems which are substituted by a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as (c) substantive dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as described, for example, in EP-A2-998 908, to which at this point explicit reference is made to claims 6 to 11.
Bevorzugte kationische direktziehende Farbstoffe der Gruppe (c) sind insbesondere die folgenden Verbindungen:Preferred cationic direct dyes of group (c) are in particular the following compounds:
Figure imgf000017_0001
CH3SO4 "
Figure imgf000017_0001
CH 3 SO 4 "
Figure imgf000017_0002
er
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000017_0002
he
Figure imgf000018_0001
Figure imgf000019_0001
Die Verbindungen der Formeln (DZ1), (DZ3) und (DZ5), die auch unter den Bezeichnungen Basic Yellow 87, Basic Orange 31 und Basic Red 51 bekannt sind, sind ganz besonders bevorzugte kationische direktziehende Farbstoffe der Gruppe (c).The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic direct dyes of group (c).
Die kationischen direktziehenden Farbstoffe, die unter dem Warenzeichen Arianor® vertrieben werden, sind erfindungsgemäß ebenfalls ganz besonders bevorzugte kationische direktziehende Farbstoffe.The cationic direct dyes, which are sold under the trademark Arianor ® are, according to the invention also very particularly preferred cationic direct dyes.
Die erfindungsgemäßen Mittel gemäß dieser Ausführungsform enthalten die direktziehenden Farbstoffe bevorzugt in einer Menge von 0,01 bis 20 Gew.-%, bezogen auf das gesamte Zweikomponentenmittel.The agents according to the invention in this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total two-component agent.
Weiterhin können die erfindungsgemäßen Zubereitungen auch in der Natur vorkommende Farbstoffe wie sie beispielsweise in Henna rot, Henna neutral, Henna schwarz, Kamillenblüte, Sandelholz, schwarzem Tee, Faulbaumrinde, Salbei, Blauholz, Krappwurzel, Catechu, Sedre und Alkannawurzel enthalten sind, enthalten.Furthermore, the preparations according to the invention can also contain naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.
Es ist nicht erforderlich, dass die Oxidationsfarbstoffvorprodukte oder die direktziehenden Farbstoffe jeweils einheitliche Verbindungen darstellen. Vielmehr können in den erfindungsgemäßen Haarfärbemitteln, bedingt durch die Herstellungsverfahren für die einzelnen Farbstoffe, in untergeordneten Mengen noch weitere Komponenten enthalten sein, soweit diese nicht das Färbeergebnis nachteilig beeinflussen oder aus anderen Gründen, z.B. toxikologischen, ausgeschlossen werden müssen.It is not necessary that the oxidation dye precursors or the substantive dyes each represent uniform compounds. Rather, the hair colorants according to the invention, due to the production process for the individual dyes, may also contain minor components in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.
Bezüglich der in den erfindungsgemäßen Zweikomponentenmitteln einsetzbaren Farbstoffe wird weiterhin ausdrücklich auf die Monographie Ch. Zviak, The Science of Hair Care, Kapitel 7 (Seiten 248-250; direktziehende Farbstoffe) sowie Kapitel 8, Seiten 264-267; Oxidationsfarbstoffvorprodukte), erschienen als Band 7 der Reihe "Dermatology" (Hrg.: Ch., Culnan und H. Maibach), Verlag Marcel Dekker Inc., New York, Basel, 1986, sowie das "Europäische Inventar der Kosmetik-Rohstoffe", herausgegeben von der Europäischen Gemeinschaft, erhältlich in Diskettenform vom Bundesverband Deutscher Industrie- und Handelsunternehmen für Arzneimittel, Reformwaren und Körperpflegemittel e.V., Mannheim, Bezug genommen.With regard to the dyes which can be used in the two-component agents according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European inventory of cosmetic raw materials", published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicines, Health Products and Personal Care Products, Mannheim.
Weiterhin enthalten die erfindungsgemäßen Zweikomponentenmittel in der Zubereitung (B) als erfindungswesentlichen Bestandteil mindestens einen Pflegestoff.Furthermore, the two-component agents according to the invention contain at least one care substance in the preparation (B) as an ingredient essential to the invention.
Im Rahmen einer ersten bevorzugten Ausführungsform enthält das erfindungsgemäße Zweikomponentenmittel als Pflegestoff mindestens ein kationisches Tensid.In the context of a first preferred embodiment, the two-component agent according to the invention contains at least one cationic surfactant as a care substance.
Erfindungsgemäß bevorzugt sind kationische Tenside vom Typ der quartären Ammoniumverbindungen, der Esterquats und der Amidoamine. Bevorzugte quartäre Ammoniumverbindungen sind Ammoniumhalogenide, insbesondere Chloride und Bromide, wie Alkyltri- methylammoniumchloride, Dialkyldimethylammoniumchloride und Trialkylmethyl- ammoniumchloride, z. B. Cetyltrimethylammoniumchlorid, Stearyltrimethylammonium- chlorid, Distearyldimethylammoniumchlorid, Lauryldimethylammoniumchlorid, Lauryl- dimethylbenzylammoniumchlorid und Tricetylmethylammoniumchlorid, sowie die unter den INCI-Bezeichnungen Quaternium-27 und Quaternium-83 bekannten Imidazolium-Ver- bindungen. Die langen Alkylketten der oben genannten Tenside weisen bevorzugt 10 bis 18 Kohlenstoffatome auf.Cationic surfactants of the type of the quaternary ammonium compounds, the esterquats and the amidoamines are preferred according to the invention. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the Veridungenazol known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
Bei Esterquats handelt es sich um bekannte Stoffe, die sowohl mindestens eine Esterfunktion als auch mindestens eine quartäre Ammoniumgruppe als Strukturelement enthalten. Bevorzugte Esterquats sind quaternierte Estersalze von Fettsäuren mit Trietha- nolamin, quaternierte Estersalze von Fettsäuren mit Diethanolalkylaminen und quater- nierten Estersalzen von Fettsäuren mit 1 ,2-Dihydroxypropyldialkylaminen. Solche Produkte werden beispielsweise unter den Warenzeichen Stepantex®, Dehyquart® und Armo- care® vertrieben. Die Produkte Armocare® VGH-70, ein N,N-Bis(2-Palmitoyloxyethyl)di- methylammoniumchlorid, sowie Dehyquart® F-75, Dehyquart® C-4046, Dehyquart® L80 und Dehyquart® AU-35 sind Beispiele für solche Esterquats. Die Alkylamidoamine werden üblicherweise durch Amidierung natürlicher oder synthetischer Fettsäuren und Fettsäureschnitte mit Dialkylaminoaminen hergestellt. Eine erfindungsgemäß besonders geeignete Verbindung aus dieser Substanzgruppe stellt das unter der Bezeichnung Tegoamid® S 18 im Handel erhältliche Stearamidopropyl- dimethylamin dar.Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines. Such products are sold, for example, under the trademarks Stepantex ® , Dehyquart ® and Armocare ® . The products Armocare ® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ® F-75, Dehyquart ® C-4046, Dehyquart ® L80 and Dehyquart ® AU-35 are examples of such esterquats , The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances that available under the name Tegoamid ® S 18 commercially stearamidopropyldimethylamine is dimethylamine.
Die kationischen Tenside sind in den erfindungsgemäßen Zweikomponentenmitteln bevorzugt in Mengen von 0,05 bis 10 Gew.-%, bezogen auf die gesamte Anwendungszubereitung, enthalten. Mengen von 0,1 bis 5 Gew.-% sind besonders bevorzugt.The cationic surfactants are preferably contained in the two-component compositions according to the invention in amounts of 0.05 to 10% by weight, based on the entire application preparation. Amounts of 0.1 to 5% by weight are particularly preferred.
Im Rahmen einer zweiten bevorzugten Ausführungsform der vorliegenden Erfindung enthalten die Zweikomponentenmittel als Pflegestoff mindestens ein pflegendes Polymer.In the context of a second preferred embodiment of the present invention, the two-component agents contain at least one caring polymer as a care substance.
Eine erste Gruppe der pflegenden Polymere sind die kationischen Polymere. Unter kationischen Polymeren sind erfindungsgemäß Polymere zu verstehen, welche in der Haupt- und/oder Seitenkette eine Gruppe aufweisen, welche "temporär" oder "permanent" kationisch sein kann. Als "permanent kationisch" werden erfindungsgemäß solche Polymere bezeichnet, die unabhängig vom pH-Wert des Mittels eine kationische Gruppe aufweisen. Dies sind in der Regel Polymere, die ein quartäres Stickstoffatom, beispielsweise in Form einer Ammoniumgruppe, enthalten. Bevorzugte kationische Gruppen sind quartäre Ammoniumgruppen. Insbesondere solche Polymere, bei denen die quartäre Ammoniumgruppe über eine C1-4-Kohlenwasserstoffgruppe an eine aus Acrylsäure, Methacrylsäure oder deren Derivaten aufgebaute Polymerhauptkette gebunden sind, haben sich als besonders geeignet erwiesen.A first group of caring polymers are the cationic polymers. Cationic polymers are understood according to the invention to mean polymers which have a group in the main and / or side chain which can be “temporary” or “permanent” cationic. According to the invention, polymers which have a cationic group irrespective of the pH of the composition are referred to as "permanently cationic". These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain composed of acrylic acid, methacrylic acid or their derivatives have proven to be particularly suitable.
Homopolymere der allgemeinen Formel (G1-I),Homopolymers of the general formula (G1-I),
Figure imgf000021_0001
in der R = -H oder -CH3 ist, R2, R3 und R4 unabhängig voneinander ausgewählt sind aus C1-4-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen, m = 1 , 2, 3 oder 4, n eine natürliche Zahl und X" ein physiologisch verträgliches organisches oder anorganisches Anion ist, sowie Copolymere, bestehend im wesentlichen aus den in Formel (G1-I) aufgeführten Monomereinheiten sowie nichtionogenen Monomereinheiten, sind besonders bevorzugte kationische Polymere. Im Rahmen dieser Polymere sind diejenigen erfindungsgemäß bevorzugt, für die mindestens eine der folgenden Bedingungen gilt: R1 steht für eine Methylgruppe R2, R3 und R4 stehen für Methylgruppen m hat den Wert 2.
Figure imgf000021_0001
in which R = -H or -CH 3 , R 2 , R 3 and R 4 are independently selected from C 1-4 alkyl, alkenyl or hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X "is a physiologically compatible organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (G1-I) and nonionic monomer units are particularly preferred cationic polymers. In the context of these polymers, those are preferred according to the invention for which at least one of the following conditions applies: R 1 stands for a methyl group R 2 , R 3 and R 4 stand for methyl groups m has the value 2.
Als physiologisch verträgliche Gegenionen X" kommen beispielsweise Halogenidionen, Sulfationen, Phosphationen, Methosulfationen sowie organische Ionen wie Lactat-, Citrat-, Tartrat- und Acetationen in Betracht. Bevorzugt sind Halogenidionen, insbesondere Chlorid.Suitable physiologically acceptable counterions X " are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Halide ions, in particular chloride, are preferred.
Ein besonders geeignetes Homopolymer ist das, gewünschtenfalls vernetzte, Poly(meth- acryloyloxyethyltrimethylammoniumchlorid) mit der INCI-Bezeichnung Polyquaternium-37. Die Vernetzung kann gewünschtenfalls mit Hilfe mehrfach olefinisch ungesättigter Verbindungen, beispielsweise Divinylbenzol, Tetraallyloxyethan, Methylenbisacrylamid, Diallylether, Polyallylpoiyglycerylether, oder Allylethern von Zuckern oder Zuckerderivaten wie Erythritol, Pentaerythritol, Arabitol, Mannitol, Sorbitol, Sucrose oder Glucose erfolgen. Methylenbisacrylamid ist ein bevorzugtes Vernetzungsagens.A particularly suitable homopolymer is, if desired crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. If desired, the crosslinking can be carried out with the aid of polyolefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ether, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylene bisacrylamide is a preferred crosslinking agent.
Das Homopolymer wird bevorzugt in Form einer nichtwäßrigen Polymerdispersion, die einen Polymeranteil nicht unter 30 Gew.-% aufweisen sollte, eingesetzt. Solche Polymerdispersionen sind unter den Bezeichnungen Salcare® SC 95 (ca. 50 % Polymeranteil, weitere Komponenten: Mineralöl (INCI-Bezeichnung: Mineral Oil) und Tridecyl-polyoxypro- pylen-polyoxyethylen-ether (INCI-Bezeichnung: PPG-1-Trideceth-6)) und Salcare® SC 96 (ca. 50 % Polymeranteil, weitere Komponenten: Mischung von Diestern des Propylengly- kols mit einer Mischung aus Capryl- und Caprinsäure (INCI-Bezeichnung: Propylene Gly- col Dicaprylate/Dicaprate) und Tridecyl-polyoxypropylen-polyoxyethylen-ether (INCI- Bezeichnung: PPG-1-Trideceth-6)) im Handel erhältlich.The homopolymer is preferably used in the form of a non-aqueous polymer dispersion which should not have a polymer content below 30% by weight. Such polymer dispersions are available under the names Salcare ® SC 95 (approx. 50% polymer content, further components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1-Trideceth- 6)) and Salcare ® SC 96 (approx. 50% polymer content, further components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: Propylene Glycol dicaprylate / Dicaprate) and tridecyl polyoxypropylene polyoxyethylene ether (INCI name: PPG-1-Trideceth-6)) commercially available.
Copolymere mit Monomereinheiten gemäß Formel (G1-I) enthalten als nichtionogene Monomereinheiten bevorzugt Acrylamid, Methacrylamid, Acrylsäure-Cι-4-alkylester und Methacrylsäure-C1-4-alkylester. Unter diesen nichtionogenen Monomeren ist das Acrylamid besonders bevorzugt. Auch diese Copolymere können, wie im Falle der Homopo- lymere oben beschrieben, vernetzt sein. Ein erfindungsgemäß bevorzugtes Copolymer ist das vernetzte Acrylamid-Methacryloyloxyethyltrimethylammoniumchlorid-Copolymer. Solche Copolymere, bei denen die Monomere in einem Gewichtsverhältnis von etwa 20:80 vorliegen, sind im Handel als ca. 50 %ige nichtwäßrige Polymerdispersion unter der Bezeichnung Salcare® SC 92 erhältlich.Copolymers with monomer units according to formula (G1-I) preferably contain acrylamide, methacrylamide, C 4 -4 alkyl acrylate and C 1-4 alkyl methacrylate as nonionic monomer units. Among these nonionic monomers, acrylamide is particularly preferred. As in the case of the homopolymers described above, these copolymers can also be crosslinked. A preferred copolymer according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ® SC 92nd
Weitere bevorzugte kationische Polymere sind beispielsweiseOther preferred cationic polymers are, for example
- quatemisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat® und Polymer JR® im Handel erhältlich sind. Die Verbindungen Celquat® H 100, Celquat® L 200 und Polymer JR®400 sind bevorzugte quaternierte Cellulose-Derivate,- Quaternized cellulose derivatives, as are commercially available under the names Celquat ® and Polymer JR ® . The compounds Celquat ® H 100, Celquat ® L 200 and Polymer JR ® 400 are preferred quaternized cellulose derivatives,
- kationische Alkylpolyglycoside gemäß der DE-PS 44 13 686,cationic alkyl polyglycosides according to DE-PS 44 13 686,
- kationiserter Honig, beispielsweise das Handelsprodukt Honeyquat® 50,cationized honey, for example the commercial product Honeyquat ® 50,
- kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosme- dia®Guar und Jaguar® vertriebenen Produkte,cationic guar derivatives, such as, in particular, the products sold under the trade names Cosmedia ® Guar and Jaguar ® ,
- Polysiloxane mit quartären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodi- methicon), Dow Corning® 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt), diquaternäre Polydimethylsiloxane, Quaternium-80),- polysiloxanes containing quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized Trimethylsilylamodi- methicone), Dow Corning ® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone ), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt), diquaternary polydimethylsiloxanes, Quaternium-80),
- polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Ami- den von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat®550 (Dimethyldiallylammoni- umchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere,- Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat ® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,
- Copolymere des Vinylpyrrolidons mit quatemierten Derivaten des Dialkylaminoal- kylacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinyl- pyrrolidon-Dimethylaminoethylmethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat®734 und Gafquat®755 im Handel erhältlich,- Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino alkyl acrylate and methacrylate, such as vinyl pyrrolidone-dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ® 734 and Gafquat ® 755,
- Vinylpyrrolidon-Vinylimidazoliummethochlorid-Copolymere, wie sie unter den Bezeichnungen Luviquat® FC 370, FC 550, FC 905 und HM 552 angeboten werden,Vinylpyrrolidone-vinylimidazolium methochloride copolymers, as are offered under the names Luviquat ® FC 370, FC 550, FC 905 and HM 552,
- quaternierter Polyvinylalkohol,- quaternized polyvinyl alcohol,
- sowie die unter den Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquatemium 18 und Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Gleichfalls als kationische Polymere eingesetzt werden können die unter den Bezeichnungen Polyquatemium-24 (Handelsprodukt z. B. Quatrisoft® LM 200), bekannten Polymere. Ebenfalls erfindungsgemäß verwendbar sind die Copolymere des Vinylpyrrolidons, wie sie als Handelsprodukte Copolymer 845 (Hersteller: ISP), Gaffix® VC 713 (Hersteller: ISP), Gafquat®ASCP 1011 , Gafquat®HS 110, Luviquat®8155 und Luviquat® MS 370 erhältlich sind.- And the known under the names Polyquaternium 2, Polyquaternium 17, Polyquatemium 18 and Polyquaternium 27 polymers with quaternary nitrogen atoms in the main polymer chain. Can be used as cationic polymers (. B. commercial product, Quatrisoft ® LM 200) under the designations Polyquaternium-24, known polymers. Likewise usable according to the invention are the copolymers of vinyl pyrrolidone, such as those available as commercial products Copolymer 845 (manufacturer: ISP), Gaffix ® VC 713 (manufacturer: ISP), Gafquat ® ASCP 1011, Gafquat ® HS 110, Luviquat ® 8155 and Luviquat ® MS 370 are.
Weitere erfindungsgemäß einsetzbare kationische Polymere sind die sogenannten "temporär kationischen" Polymere. Diese Polymere enthalten üblicherweise eine Aminogruppe, die bei bestimmten pH-Werten als quartäre Ammoniumgruppe und somit kationisch vorliegt. Bevorzugt sind beispielsweise Chitosan und dessen Derivate, wie sie beispielsweise unter den Handelsbezeichnungen Hydagen® CMF, Hydagen® HCMF, Kytamer® PC und Chitolam® NB/101 im Handel frei verfügbar sind.Further cationic polymers that can be used according to the invention are the so-called “temporarily cationic” polymers. These polymers usually contain an amino group which is present as a quaternary ammonium group at certain pH values and is therefore cationic. Preferably, for example, are chitosan and its derivatives, such as 101 are freely available commercially, for example under the trade names Hydagen CMF ®, Hydagen HCMF ®, Kytamer ® PC and Chitolam ® NB /.
Erfindungsgemäß bevorzugt eingesetzte kationische Polymere sind kationische Cellulose- Derivate und Chitosan und dessen Derivate, insbesondere die Handelsprodukte Polymer®JR 400, Hydagen® HCMF und Kytamer® PC, kationische Guar-Derivate, kationische Honig-Derivate, insbesondere das Handelsprodukt Honeyquat® 50, kationische Alkylpoiyglycodside gemäß der DE-PS 44 13 686 und Polymere vom Typ Polyquatemium-37.According to the invention cationic polymers employed are cationic cellulose derivatives and chitosan and its derivatives, in particular the commercial products Polymer ® JR 400, Hydagen ® HCMF and Kytamer ® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat ® 50, cationic Alkyl polyglycodides according to DE-PS 44 13 686 and polymers of the type Polyquatemium-37.
Weiterhin sind kationiserte Proteinhydrolysate zu den kationischen Polymeren zu zählen, wobei das zugrunde liegende Proteinhydrolysat vom Tier, beispielsweise aus Collagen, Milch oder Keratin, von der Pflanze, beispielsweise aus Weizen, Mais, Reis, Kartoffeln, Soja oder Mandeln, von marinen Lebensformen, beispielsweise aus Fischcollagen oder Algen, oder biotechnologisch gewonnenen Proteinhydrolysaten, stammen kann. Die den erfindungsgemäßen kationischen Derivaten zugrunde liegenden Proteinhydrolysate können aus den entsprechenden Proteinen durch eine chemische, insbesondere alkalische oder saure Hydrolyse, durch eine enzymatische Hydrolyse und/oder eine Kombination aus beiden Hydrolysearten gewonnen werden. Die Hydrolyse von Proteinen ergibt in der Regel ein Proteinhydrolysat mit einer Molekulargewichtsverteilung von etwa 100 Dalton bis hin zu mehreren tausend Dalton. Bevorzugt sind solche kationischen Proteinhydrolysate, deren zugrunde liegender Proteinanteil ein Molekulargewicht von 100 bis zu 25000 Dalton, bevorzugt 250 bis 5000 Dalton aufweist. Weiterhin sind unter kationischen Proteinhydrolysaten quaternierte Aminosäuren und deren Gemische zu verstehen. Die Quaternisierung der Proteinhydrolysate oder der Aminosäuren wird häufig mittels quartären Ammoniumsalzen wie beispielsweise N,N-Dimethyl-N-(n-Alkyl)-N-(2- hydroxy-3-chloro-n-propyl)-ammoniumhalogeniden durchgeführt. Weiterhin können die kationischen Proteinhydrolysate auch noch weiter derivatisiert sein. Als typische Beispiele für die erfindungsgemäßen kationischen Proteinhydrolysate und -derivate seien die unter den INCI - Bezeichnungen im "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17th Street, N.W., Suite 300, Washington, DC 20036-4702) genannten und im Handel erhältlichen Produkte genannt: Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl/Myristyl Ether HCI, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen,Furthermore, cationized protein hydrolyzates are to be counted among the cationic polymers, the underlying protein hydrolyzate being derived from animals, for example from collagen, milk or keratin, from plants, for example from wheat, corn, rice, potatoes, soy or almonds, from marine life forms, for example from fish collagen or algae, or biotechnologically obtained protein hydrolyzates. The protein hydrolysates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate with a molecular weight distribution of approximately 100 daltons up to several thousand daltons. Preferred cationic protein hydrolyzates are those whose underlying protein content has a molecular weight of 100 to 25,000 Daltons, preferably 250 to 5000 Daltons. Cationic protein hydrolyzates also include quaternized amino acids and their mixtures. The quaternization of protein hydrolyzates or amino acids becomes common using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolyzates can also be further derivatized. As typical examples of the inventive cationic protein hydrolysates and derivatives are under the INCI - th names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 Street, NW, Suite 300 , Washington, DC 20036-4702) and commercially available products: Cocodimonium hydroxypropyl hydrolyzed collagen, Cocodimonium hydroxypropyl hydrolyzed casein, Cocodimonium hydroxypropyl hydrolyzed collagen, Cocodimonium hydroxypropyl hydrolyzed hair keratin, Cocodimonium hydroxypropyl hydrolyzed keratin, Cocodimonium hydroxypropyl hydrolyzed Rice Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCI, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen,
Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein/Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein/Siloxysilicate, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quatemium-79 Hydrolyzed Milk Protein, Quaternium- 79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilypropyl Laurdyl Lauryl Protein, Sildoxyl Silicyl Lauryl Hydroxypropyl hydrolyzed wheat protein / siloxysilicates, lauryldimonium hydroxypropyl hydrolyzed casein, lauryldimonium hydroxypropyl hydrolyzed collagen, lauryldimonium hydroxypropyl hydrolyzed keratin, lauryldimonium hydroxypropyl hydrolyzed soy protein, steardimonium hydroxypropyl hydrolyzed casein, steardimonium hydroxypropyl hydrolydimethyl hydroxypropyl hydrolydimethyl hydroxypropyl hydrolyzedimonium hydroxypropyl hydrolydimedium hydroxypropyl hydrolydimethyl hydroxypropyl hydrolyzedimide, Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxyprop yl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quatemium-79 Hydrolyzed Milk Protein, Quaternium- 79 Hydrolyzed Soy Protein 79 Hydrolyzed Wheat Protein.
Ganz besonders bevorzugt sind die kationischen Proteinhydrolysate und -derivate auf pflanzlicher Basis. Weitere erfindungsgemäß einsetzbare pflegende Polymere sind die in der britischen Offenlegungsschrift 2 104 091 , der europäischen Offenlegungsschrift 47 714, der europäischen Offenlegungsschrift 217274, der europäischen Offenlegungsschrift 283 817 und der deutschen Offenlegungsschrift 28 17 369 genannten amphoteren Verbindungen.The plant-based cationic protein hydrolyzates and derivatives are very particularly preferred. Further care polymers that can be used according to the invention are the amphoteric compounds mentioned in British Patent Application 2 104 091, European Patent Application 47 714, European Patent Application 217274, European Patent Application 283 817 and German Patent Application 28 17 369.
Bevorzugt eingesetzte amphotere Polymere sind solche Polymerisate, die sich im wesentlichen zusammensetzen ausAmphoteric polymers which are preferably used are those polymers which essentially consist of one another
(a) Monomeren mit quartären Ammoniumgruppen der allgemeinen Formel (II), R1-CH=CR2-CO-Z-(CnH2n)-N(+)R3R4R5 A("> (II) in der R1 und R2 unabhängig voneinander stehen für Wasserstoff oder eine Methylgruppe und R3, R4 und R5 jeweils unabhängig voneinander für eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, Z eine NH-Gruppe oder ein Sauerstoffatom, n eine ganze Zahl von 2 bis 5 und A das Anion einer organischen oder anorganischen Säure ist, und(a) Monomers with quaternary ammonium groups of the general formula (II), R 1 -CH = CR 2 -CO-Z- (C n H 2n ) -N (+) R 3 R 4 R 5 A (" > (II) in which R 1 and R 2 independently represent hydrogen or a methyl group and R 3 , R 4 and R 5 each independently represent an alkyl group having 1 to 4 carbon atoms, Z an NH group or an oxygen atom, n is an integer from 2 to 5 and A is the anion of an organic or inorganic acid, and
(b) monomeren Carbonsäuren der allgemeinen Formel (III), R6-CH=CR7-COOH (III) in denen R6 und R7 unabhängig voneinander für Wasserstoff oder eine Methylgruppe stehen.(b) monomeric carboxylic acids of the general formula (III), R 6 -CH = CR 7 -COOH (III) in which R 6 and R 7 independently of one another represent hydrogen or a methyl group.
Diese Verbindungen können sowohl direkt als auch in Salzform, die durch Neutralisation der Polymerisate, beispielsweise mit einem Alkalihydroxid, erhalten wird, erfindungsgemäß eingesetzt werden. Bezüglich der Einzelheiten der Herstellung dieser Polymerisate wird ausdrücklich auf den Inhalt der deutschen Offenlegungsschrift 39 29 973 Bezug genommen. Ganz besonders bevorzugt sind solche Polymerisate, bei denen Monomere des Typs (a) eingesetzt werden, bei denen R3, R4 und R5 Methylgruppen sind, Z eine NH- Gruppe und A(_) ein Halogenid-, Methoxysulfat- oder Ethoxysulfat-Ion ist; Acrylamido- propyltrimethyl-ammoniumchlorid ist ein besonders bevorzugtes Monomeres (a). Als Monomeres (b) für die genannten Polymerisate wird bevorzugt Acrylsäure verwendet.According to the invention, these compounds can be used both directly and in salt form, which is obtained by neutralizing the polymers, for example with an alkali metal hydroxide. With regard to the details of the preparation of these polymers, reference is expressly made to the content of German laid-open specification 39 29 973. Those polymers in which monomers of type (a) are used, in which R 3 , R 4 and R 5 are methyl groups, Z is an NH group and A (_) is a halide, methoxysulfate or ethoxysulfate, Ion is; Acrylamido propyl trimethyl ammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably used as monomer (b) for the polymers mentioned.
Die erfindungsgemäßen Zweikomponentenmittel enthalten die pflegenden, kationischen Polymere in bevorzugter Weise in einer Menge von 0,01 bis 5 Gew.-%, insbesondere in einer Menge von 0,1 bis 2 Gew.-%, jeweils bezogen auf die gesamte Anwendungszubereitung.The two-component agents according to the invention preferably contain the caring, cationic polymers in an amount of 0.01 to 5% by weight, in particular in an amount of 0.1 to 2% by weight, based in each case on the entire application preparation.
Im Rahmen einer dritten bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zweikomponentenmittel mindestens einen UV-Filter. Die erfindungsgemäß geeigneten UV-Filter unterliegen hinsichtlich ihrer Struktur und ihrer physikalischen Eigenschaften keinen generellen Einschränkungen. Vielmehr eignen sich alle im Kosmetikbereich einsetzbaren UV-Filter, deren Absorptionsmaximum im UVA(315-400 nm)-, im UVB(280- 315nm)- oder im UVC(<280 nm)-Bereich liegt. UV-Filter mit einem Absorptionsmaximum im UVB-Bereich, insbesondere im Bereich von etwa 280 bis etwa 300 nm, sind besonders bevorzugt.In the context of a third preferred embodiment, the two-component agents according to the invention contain at least one UV filter. The suitable according to the invention UV filters are not subject to any general restrictions with regard to their structure and physical properties. Rather, all UV filters that can be used in the cosmetics sector are suitable, the absorption maximum of which lies in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC (<280 nm) range. UV filters with an absorption maximum in the UVB range, in particular in the range from approximately 280 to approximately 300 nm, are particularly preferred.
Die erfindungsgemäß bevorzugten UV-Filter können beispielsweise ausgewählt werden aus substituierten Benzophenonen, p-Aminobenzoesäureestern, Diphenylacrylsäure- estern, Zimtsäureestern, Salicylsäureestern, Benzimidazoien und o-Aminobenzoesäure- estern.The UV filters preferred according to the invention can be selected, for example, from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoien and o-aminobenzoic acid esters.
Beispiele für erfindungsgemäß verwendbare UV-Filter sind 4-Amino-benzoesäure, N,N,N- Trimethyl-4-(2-oxoborn-3-ylidenmethyl)anilin-methylsulfat, 3,3,5-Trimethyl-cyclohexyl- salicylat (Homosalate), 2-Hydroxy-4-methoxy-benzophenon (Benzophenone-3; Uvinul®M 40, Uvasorb®MET, Neo Heliopan®BB, Eusolex®4360), 2-Phenylbenzimidazol-5-sulfon- säure und deren Kalium-, Natrium- und Triethanolaminsalze (Phenylbenzimidazole sulfonic acid; Parsol®HS; Neo Heliopan®Hydro), 3,3'-(1 ,4-Phenylendimethylen)-bis(7,7- dimethyl-2-oxo-bicyclo-[2.2.1]hept-1-yl-methan-sulfonsäure) und deren Salze, 1-(4-tert.- Butylphenyl)-3-(4-methoxyphenyl)-propan-1 ,3-dion (Butyl methoxydibenzoylmethane; Parsol®1789, Eusolex®9020), α-(2-Oxoborn-3-yliden)-toluol-4-sulfonsäure und deren Salze, ethoxylierte 4-Aminobenzoesäure-ethylester (PEG-25 PABA; Uvinul®P 25), 4-Di- methylaminobenzoesäure-2-ethylhexylester (Octyl Dimethyl PABA; Uvasorb®DMO, Escalol®507, Eusolex®6007), Salicylsäure-2-ethylhexylester (Octyl Salicylat; Escalol®587, Neo Heliopan®OS, Uvinul®018), 4-Methoxyzimtsäure-isopentylester (Isoamyl p-Methoxy- cinnamate; Neo Heliopan®E 1000), 4-Methoxyzimtsäure-2-ethylhexyl-ester (Octyl Methoxycinnamate; Parsol®MCX, Escalol®557, Neo Heliopan®AV), 2-Hydroxy-4-methoxy- benzophenon-5-sulfonsäure und deren Natriumsalz (Benzophenone-4; Uvinul®MS 40; Uvasorb®S 5), 3-(4'-Methylbenzyliden)-D,L-Campher (4-Methylbenzylidene camphor; Parsol®5000, Eusolex®630O), 3-Benzyliden-campher (3-Benzylidene camphor), 4-lsopro- pylbenzylsalicylat, 2,4,6-Trianilino-(p-carbo-2'-ethylhexyl-1 '-oxi)-1 ,3,5-triazin, 3-lmidazoi-4- yl-acrylsäure und deren Ethylester, Polymere des N-{(2 und 4)-[2-oxoborn-3-yliden- methyl]benzyl}-acrylamids, 2,4-Dihydroxybenzophenon (Benzophenone-1; Uvasorb®20 H, Uvinul®400), 1 ,1'-DiphenylacryIonitrilsäure-2-ethylhexyl-ester (Octocrylene; Eusolex®OCR, Neo Heliopan®Type 303, Uvinul®N 539 SG), o-Aminobenzoesäure-menthylester (Menthyl Anthranilate; Neo Heliopan®MA), 2,2',4,4'-Tetrahydroxybenzophenon (Benzophenone-2; Uvinul®D-50), 2,2'-Dihydroxy-4,4'-dimethoxybenzophenon (Benzophenone-6), 2,2'- Dihydroxy-4,4'-dimethoxybenzophenon-5-natriumsulfonat und 2-Cyano-3,3-diphenylacryl- säure-2'-ethylhexylester. Bevorzugt sind 4-Amino-benzoesäure, N,N,N-Trimethyl-4-(2- oxoborn-3-ylidenmethyl)anilin-methylsulfat, 3,3,5-Trimethyl-cyclohexylsalicylat, 2-Hydroxy- 4-methoxy-benzophenon, 2-PhenylbenzimidazoI-5-sulfonsäure und deren Kalium-, Natrium- und Triethanolaminsalze, 3,3'-(1 ,4-Phenylendimethylen)-bis(7,7-dimethyl-2-oxo- bicyclo-[2.2.1]hept-1-yl-methan-sulfonsäure) und deren Salze, 1-(4-tert.-Butylphenyl)-3-(4- methoxyphenyl)-propan-1,3-dion, α-(2-Oxoborn-3-yliden)-toluol-4-sulfonsäure und deren Salze, ethoxylierte 4-Aminobenzoesäure-ethylester, 4-DimethyIaminobenzoesäure-2- ethylhexylester, Salicylsäure-2-ethylhexylester, 4-Methoxyzimtsäure-isopentylester, 4- Methoxyzimtsäure-2-ethylhexyl-ester, 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure und deren Natriumsalz, 3-(4'-Methylbenzyliden)-D,L-Campher, 3-Benzyliden-campher, 4- Isopropylbenzylsalicylat, 2,4,6-Trianilino-(p-carbo-2'-ethyIhexyl-1 '-oxi)-1 ,3,5-triazin, 3- lmidazol-4-yl-acrylsäure und deren Ethylester, Polymere des N-{(2 und 4)-[2-oxobom-3- ylidenmethyl]benzyl}-acrylamid. Erfindungsgemäß ganz besonders bevorzugt sind 2- Hydroxy-4-methoxy-benzophenon, 2-Phenylbenzimidazol-5-sulfonsäure und deren Kalium-, Natrium- und Triethanolaminsalze, 1-(4-tert.-Butylphenyl)-3-(4-methoxyphenyl)- propan-1,3-dion, 4-Methoxyzimtsäure-2-ethylhexyl-ester und 3-(4'-Methylbenzyliden)-D,L- Campher.Examples of UV filters which can be used according to the invention are 4-amino-benzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline-methyl sulfate, 3,3,5-trimethyl-cyclohexyl-salicylate (homosalates ), 2-Hydroxy-4-methoxy-benzophenone (Benzophenone-3; Uvinul ® M 40, Uvasorb ® MET, Neo Heliopan ® BB, Eusolex ® 4360), 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium - and triethanolamine salts (phenylbenzimidazole sulfonic acid; Parsol ® HS; Neo Heliopan ® Hydro), 3,3 '- (1, 4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxo-bicyclo- [2.2.1] hept-1-yl-methane-sulfonic acid) and salts thereof, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione (butyl methoxydibenzoylmethane; Parsol ® 1789 Eusolex ® 9020), α- (2-oxoborn-3-ylidene) toluene-4-sulfonic acid and its salts, ethoxylated ethyl 4-aminobenzoate (PEG-25 PABA; Uvinul ® P 25), 4-dimethylaminobenzoic acid 2- ethylhexyl ester (octyl dimethyl PABA; Uvasorb ® DMO, Escalol ® 507, Eusolex ® 6007), salicylic acid -2-ethylhexyl ester (octyl salicylate; Escalol ® 587, Neo Heliopan ® OS, Uvinul ® 018), 4-methoxycinnamic acid isopentyl ester (isoamyl p-methoxycinnamate; Neo Heliopan ® E 1000), 4-methoxycinnamic acid 2-ethylhexyl ester (octyl methoxycinnamate; Parsol ® MCX , Escalol ® 557, Neo Heliopan ® AV), 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (Benzophenone-4; Uvinul ® MS 40; Uvasorb ® S 5), 3- (4'-methylbenzylidene ) -D, L-camphor (4-methylbenzylidene camphor; Parsol ® 5000, Eusolex ® 630O), 3-benzylidene-camphor (3-benzylidene camphor), 4-isopropylbenzylsalicylate, 2,4,6-trianilino- (p -carbo-2'-ethylhexyl-1 '-oxi) -1, 3,5-triazine, 3-imidazoi-4-yl-acrylic acid and its ethyl ester, polymers of N - {(2 and 4) - [2-oxoborn -3-ylidene-methyl] benzyl} -acrylamids, 2,4-dihydroxybenzophenone (Benzophenone-1; Uvasorb ® 20 H, Uvinul ® 400), 1'-1'-DiphenylacryIonitrilsäure-2-ethylhexyl-ester (Octocrylene; Eusolex ® OCR , Neo Heliopan ® Type 303, Uvinul ® N 539 SG), o-aminobenzoic acid menthyl ester (menthyl anthranilate; Neo Heliopan ® MA), 2,2 ', 4,4'-tetrahydroxybenzophenone (Benzophenone-2; Uvinul ® D-50), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Benzophenone-6), 2, 2'-Dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate and 2-cyano-3,3-diphenylacrylic acid 2'-ethylhexyl ester. 4-Amino-benzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline-methyl sulfate, 3,3,5-trimethyl-cyclohexylsalicylate, 2-hydroxy-4-methoxy-benzophenone are preferred , 2-PhenylbenzimidazoI-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 3,3 '- (1,4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxobicyclo- [2.2.1] hept-1-yl-methanesulfonic acid) and their salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione, α- (2-oxoborn-3- ylidene) -toluene-4-sulfonic acid and its salts, ethoxylated ethyl 4-aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-ethylhexyl salicylate, isopentyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, 2 -Hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 3- (4'-methylbenzylidene) -D, L-camphor, 3-benzylidene-camphor, 4- isopropylbenzylsalicylate, 2,4,6-trianilino- (p- carbo-2'-ethylhexyl-1 '-oxy) -1, 3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of N - {(2nd and 4) - [2-oxobom-3-ylidenemethyl] benzyl} acrylamide. According to the invention, 2-hydroxy-4-methoxy-benzophenone, 2-phenylbenzimidazole-5-sulfonic acid and their potassium, sodium and triethanolamine salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) are very particularly preferred. - Propane-1,3-dione, 4-methoxycinnamic acid 2-ethylhexyl ester and 3- (4'-methylbenzylidene) -D, L-camphor.
Bevorzugt sind solche UV-Filter, deren molarer Extinktionskoeffizient am Absorptionsmaximum oberhalb von 15000, insbesondere oberhalb von 20 000, liegt.Preferred UV filters are those whose molar extinction coefficient at the absorption maximum is above 15,000, in particular above 20,000.
Weiterhin wurde gefunden, dass bei strukturell ähnlichen UV-Filtern in vielen Fällen die wasserunlösliche Verbindung im Rahmen der erfindungsgemäßen Lehre die höhere Wirkung gegenüber solchen wasserlöslichen Verbindungen aufweist, die sich von ihr durch eine oder mehrere zusätzlich ionische Gruppen unterscheiden. Als wasserunlöslich sind im Rahmen der Erfindung solche UV-Filter zu verstehen, die sich bei 20 °C zu nicht mehr als 1 Gew.-%, insbesondere zu nicht mehr als 0,1 Gew.-%, in Wasser lösen. Weiterhin sollten diese Verbindungen in üblichen kosmetischen Ölkomponenten bei Raumtemperatur zu mindestens 0,1, insbesondere zu mindestens 1 Gew.-% löslich sein. Die Verwendung wasserunlöslicher UV-Filter kann daher erfindungsgemäß bevorzugt sein. Gemäß einer weiteren Ausführungsform der Erfindung sind solche UV-Filter bevorzugt, die eine kationische Gruppe, insbesondere eine quartäre Ammoniumgruppe, aufweisen.Furthermore, it was found that in structurally similar UV filters, the water-insoluble compound has, in the context of the teaching according to the invention, the higher activity than those water-soluble compounds which differ from it by one or more additional ionic groups. Within the scope of the invention, water-insoluble are those UV filters which do not dissolve in water at 20 ° C. by more than 1% by weight, in particular not more than 0.1% by weight. Furthermore, these compounds should be at least 0.1, in particular at least 1% by weight soluble in conventional cosmetic oil components at room temperature. The use of water-insoluble UV filters can therefore be preferred according to the invention. According to a further embodiment of the invention, those UV filters are preferred which have a cationic group, in particular a quaternary ammonium group.
Diese UV-Filter weisen die allgemeine Struktur U - Q auf.These UV filters have the general structure U - Q.
Der Strukturteil U steht dabei für eine UV-Strahlen absorbierende Gruppe. Diese Gruppe kann sich im Prinzip von den bekannten, im Kosmetikbereich einsetzbaren, oben genannten UV-Filtern ableiten, in dem eine Gruppe, in der Regel ein Wasserstoffatom, des UV- Filters durch eine kationische Gruppe Q, insbesondere mit einer quartären Aminofunktion, ersetzt wird.The structural part U stands for a group that absorbs UV rays. In principle, this group can be derived from the known UV filters mentioned above, which can be used in the cosmetics sector, in which a group, usually a hydrogen atom, of the UV filter is replaced by a cationic group Q, in particular with a quaternary amino function ,
Verbindungen, von denen sich der Strukturteil U ableiten kann, sind beispielsweiseConnections from which the structural part U can be derived are, for example
- substituierte Benzophenone,- substituted benzophenones,
- p-Aminobenzoesäureester,p-aminobenzoic acid ester,
- Diphenylacrylsäureester,- diphenylacrylic acid ester,
- Zimtsäureester, Salicylsäureester,- cinnamic acid esters, salicylic acid esters,
- Benzimidazole und- benzimidazoles and
- o-Aminobenzoesäureester.o-aminobenzoic acid esters.
Strukturteile U, die sich vom Zimtsäureamid oder vom N,N-Dimethylamino-benzoesäu- reamid ableiten, sind erfindungsgemäß bevorzugt.Structural parts U which are derived from cinnamic acid amide or from N, N-dimethylamino-benzoic acid amide are preferred according to the invention.
Die Strukturteile U können prinzipiell so gewählt werden, dass das Absorptionsmaximum der UV-Filter sowohl im UVA(315-40O nm)-, als auch im UVB(280-315nm)- oder im UVC(<280 nm)-Bereich liegen kann. UV-Filter mit einem Absorptionsmaximum im UVB- Bereich, insbesondere im Bereich von etwa 280 bis etwa 300 nm, sind besonders bevorzugt.The structural parts U can in principle be selected so that the absorption maximum of the UV filter can be both in the UVA (315-40O nm) and UVB (280-315 nm) or in the UVC (<280 nm) range. UV filters with an absorption maximum in the UVB range, in particular in the range from approximately 280 to approximately 300 nm, are particularly preferred.
Weiterhin wird der Strukturteil U, auch in Abhängigkeit von Strukturteil Q, bevorzugt so gewählt, dass der molare Extinktionskoeffizient des UV-Filters am Absorptionsmaximum oberhalb von 15 000, insbesondere oberhalb von 20 000, liegt.Furthermore, structural part U, also depending on structural part Q, is preferably selected such that the molar extinction coefficient of the UV filter at the absorption maximum is above 15,000, in particular above 20,000.
Der Strukturteil Q enthält als kationische Gruppe bevorzugt eine quartäre Ammoniumgruppe. Diese quartäre Ammoniumgruppe kann prinzipiell direkt mit dem Strukturteil U verbunden sein, so dass der Strukturteil U einen der vier Substituenten des positiv geladenen Stickstoffatomes darstellt. Bevorzugt ist jedoch einer der vier Substituenten am positiv geladenen Stickstoffatom eine Gruppe, insbesondere eine Alkylengruppe mit 2 bis 6 Kohlenstoffatomen, die als Verbindung zwischen dem Strukturteil U und dem positiv geladenen Stickstoffatom fungiert.The structural part Q preferably contains a quaternary ammonium group as the cationic group. This quaternary ammonium group can in principle directly with the structural part U be connected so that the structural part U represents one of the four substituents of the positively charged nitrogen atom. However, one of the four substituents on the positively charged nitrogen atom is preferably a group, in particular an alkylene group having 2 to 6 carbon atoms, which functions as a connection between the structural part U and the positively charged nitrogen atom.
Vorteilhafterweise hat die Gruppe Q die allgemeine Struktur -(CH2)X-N+R1R2R3 X", in der x steht für eine ganze Zahl von 1 bis 4, R1 und R2 unabhängig voneinander stehen für C1-4- Alkylgruppen, R3 steht für eine C1-22-Alkylgruppe oder eine Benzylgruppe und X" für ein physiologisch verträgliches Anion. Im Rahmen dieser allgemeinen Struktur steht x bevorzugt für die Zahl 3, R1 und R2 jeweils für eine Methylgruppe und R3 entweder für eine Methylgruppe oder eine gesättigte oder ungesättigte, lineare oder verzweigte Kohlenwasserstoffkette mit 8 bis 22, insbesondere 10 bis 18, Kohlenstoffatomen.Advantageously, the group Q has the general structure - (CH 2 ) X -N + R 1 R 2 R 3 X " , in which x represents an integer from 1 to 4, R 1 and R 2 independently of one another represent C 1 -4 - alkyl groups, R 3 stands for a C 1-22 alkyl group or a benzyl group and X " for a physiologically acceptable anion. Within the framework of this general structure, x preferably stands for the number 3, R 1 and R 2 each for a methyl group and R 3 either for a methyl group or a saturated or unsaturated, linear or branched hydrocarbon chain with 8 to 22, in particular 10 to 18, carbon atoms ,
Physiologisch verträgliche Anionen sind beispielsweise anorganische Anionen wie Halogenide, insbesondere Chlorid, Bromid und Fluorid, Sulfationen und Phosphationen sowie organische Anionen wie Lactat, Citrat, Acetat, Tartrat, Methosulfat und Tosylat.Physiologically compatible anions are, for example, inorganic anions such as halides, in particular chloride, bromide and fluoride, sulfate ions and phosphate ions, and organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.
Zwei bevorzugte UV-Filter mit kationischen Gruppen sind die als Handelsprodukte erhältlichen Verbindungen Zimtsäureamidopropyl-trimethylammoniumchlorid (lncroquat®UV- 283) und Dodecyl-dimethylaminobenzamidopropyl-dimethylammoniumtosylat (Escalol® HP 610).Two preferred UV filters with cationic groups are the commercially available compounds cinnamic acid-trimethylammonium chloride (lncroquat ® UV 283) and dodecyl tosylate (Escalol ® HP 610).
Selbstverständlich umfasst die erfindungsgemäße Lehre auch die Verwendung einer Kombination von mehreren UV-Filtern. Im Rahmen dieser Ausführungsform ist die Kombination mindestens eines wasserunlöslichen UV-Filters mit mindestens einem UV- Filter mit einer kationischen Gruppe bevorzugt.Of course, the teaching according to the invention also includes the use of a combination of several UV filters. In the context of this embodiment, the combination of at least one water-insoluble UV filter with at least one UV filter with a cationic group is preferred.
Die UV-Filter sind in den erfindungsgemäßen Mitteln üblicherweise in Mengen 0,01-5 Gew.-%, bezogen auf die gesamte Anwendungszubereitung, enthalten. Mengen von 0,1- 2,5 Gew.-% sind bevorzugt.The UV filters are usually contained in the agents according to the invention in amounts of 0.01-5% by weight, based on the entire application preparation. Amounts of 0.1-2.5% by weight are preferred.
Im Rahmen einer vierten bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zweikomponentenmittel als Pflegestoff mindestens ein Vitamin, ein Provitamin, eine Vitaminvorstufe und/oder eines derer Derivate. Dabei sind erfindungsgemäß solche Vitamine, Pro-Vitamine und Vitaminvorstufen bevorzugt, die üblicherweise den Gruppen A, B, C, E, F und H zugeordnet werden.In a fourth preferred embodiment, the two-component agents according to the invention contain at least one vitamin, one provitamin, one vitamin precursor and / or one of their derivatives as a care substance. Vitamins, pro-vitamins and vitamin precursors which are usually assigned to groups A, B, C, E, F and H are preferred according to the invention.
Zur Gruppe der als Vitamin A bezeichneten Substanzen gehören das Retinol (Vitamin A^ sowie das 3,4-Didehydroretinol (Vitamin A2). Das ß-Carotin ist das Provitamin des Re- tinols. Als Vitamin A-Komponente kommen erfindungsgemäß beispielsweise Vitamin A- Säure und deren Ester, Vitamin A-Aldehyd und Vitamin A-Alkohol sowie dessen Ester wie das Palmitat und das Acetat in Betracht. Die erfindungsgemäß verwendeten Zubereitungen enthalten die Vitamin A-Komponente bevorzugt in Mengen von 0,05-1 Gew.-%, bezogen auf die gesamte Anwendungszubereitung.Retinol (vitamin A ^ and 3,4-didehydroretinol (vitamin A 2 ) belong to the group of substances called vitamin A. β-carotene is the provitamin of retinol. According to the invention, vitamin A comes as vitamin A component Acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as palmitate and acetate are considered The preparations used according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight , based on the entire application preparation.
Zur Vitamin B-Gruppe oder zu dem Vitamin B-Komplex gehören u. a.The vitamin B group or the vitamin B complex include u. a.
- Vitamin B-i (Thiamin)- Vitamin B-i (thiamine)
- Vitamin B2 (Riboflavin)- Vitamin B 2 (riboflavin)
- Vitamin B3. Unter dieser Bezeichnung werden häufig die Verbindungen Nicotinsäure und Nicotinsäureamid (Niacinamid) geführt. Elf indungsgemäß bevorzugt ist das Nico- tinsäureamid, das in den erfindungsgemäßen IVlitteln bevorzugt in Mengen von 0,05 bis 1 Gew.-%, bezogen auf die gesamte Anwendungszubereitung, enthalten ist.- Vitamin B 3 . The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. Eleven preferred according to the invention is the nicotinic acid amide, which is preferably contained in the IV compositions according to the invention in amounts of 0.05 to 1% by weight, based on the entire application preparation.
- Vitamin B5 (Pantothensäure, Panthenol und Pantolacton). Im Rahmen dieser Gruppe wird bevorzugt das Panthenol und/oder Pantolacton eingesetzt. Erfindungsgemäß einsetzbare Derivate des Panthenols sind insbesondere die Ester und Ether des Panthenols sowie kationisch derivatisierte Panthenole. Einzelne Vertreter sind beispielsweise das Panthenoltriacetat, der Panthenolmonoethylether und dessen Monoacetat sowie die in der WO 92/13829 offenbarten kationischen Panthenolderivate. Die genannten Verbindungen des Vitamin B5-Typs sind in den erfindungsgemäßen Mitteln bevorzugt in Mengen von 0,05 - 10 Gew.-%, bezogen auf die gesamte Anwendungszubereitung, enthalten. Mengen von 0,1 - 5 Gew.-% sind besonders bevorzugt.- Vitamin B 5 (pantothenic acid, panthenol and pantolactone). Within this group, panthenol and / or pantolactone is preferably used. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and cationically derivatized panthenols. Individual representatives are, for example, panthenol triacetate, panthenol monoethyl ether and its monoacetate and the cationic panthenol derivatives disclosed in WO 92/13829. The compounds of the vitamin B 5 type mentioned are preferably present in the agents according to the invention in amounts of 0.05-10% by weight, based on the entire application preparation. Amounts of 0.1-5% by weight are particularly preferred.
- Vitamin B6 (Pyridoxin sowie Pyridoxamin und Pyridoxal). Die genannten Verbindungen des Vitamin B6-Typs sind in den erfindungsgemäßen Mitteln bevorzugt in Mengen von 0,01 - 5 Gew.-%, bezogen auf die gesamte Anwendungszubereitung, enthalten. Mengen von 0,05 - 1 Gew.-% sind besonders bevorzugt. Vitamin C (Ascorbinsäure). Vitamin C wird in den erfindungsgemäß verwendeten Mitteln bevorzugt in Mengen von 0,1 bis 3 Gew.-%, bezogen auf die gesamte Anwendungszubereitung eingesetzt. Die Verwendung in Form des Palmitinsäureesters, der Glucoside oder Phosphate kann bevorzugt sein. Die Verwendung in Kombination mit Tocopherolen kann ebenfalls bevorzugt sein.- Vitamin B 6 (pyridoxine, pyridoxamine and pyridoxal). The compounds of the vitamin B 6 type mentioned are preferably present in the agents according to the invention in amounts of 0.01-5% by weight, based on the entire application preparation. Amounts of 0.05-1% by weight are particularly preferred. Vitamin C (ascorbic acid). Vitamin C is used in the agents used according to the invention preferably in amounts of 0.1 to 3% by weight, based on the entire application preparation. Use in the form of the palmitic acid ester, the glucosides or phosphates can be preferred. Use in combination with tocopherols may also be preferred.
Vitamin E (Tocopherole, insbesondere α-Tocopherol). Tocopherol und seine Derivate, worunter insbesondere die Ester wie das Acetat, das Nicotinat, das Phosphat und das Succinat fallen, sind in den erfindungsgemäßen Mitteln bevorzugt in Mengen von 0,05-1 Gew.-%, bezogen auf die gesamte Anwendungszubereitung, enthalten.Vitamin E (tocopherols, especially α-tocopherol). Tocopherol and its derivatives, which include in particular the esters such as acetate, nicotinate, phosphate and succinate, are preferably present in the agents according to the invention in amounts of 0.05-1% by weight, based on the entire application preparation.
Vitamin F. Unter dem Begriff "Vitamin F" werden üblicherweise essentielle Fettsäuren, insbesondere Linolsäure, Linolensäure und Arachidonsäure, verstanden.Vitamin F. The term "vitamin F" usually means essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.
Vitamin H. Als Vitamin H wird die Verbindung (3aS,4S, 6af?)-2-Oxohexahydrothienol[3,4- c ]-imidazol-4-valeriansäure bezeichnet, für die sich aber inzwischen der Trivialname Biotin durchgesetzt hat. Biotin ist in den erfindungsgemäßen Mitteln bevorzugt in Mengen von 0,0001 bis 1,0 Gew.-%, insbesondere in Mengen von 0,001 bis 0,01 Gew.-%, jeweils bezogen auf die gesamte Anwendungszubereitung enthalten.Vitamin H. The compound (3aS, 4S, 6af?) - 2-oxohexahydrothienol [3,4-c] -imidazole-4-valeric acid is called vitamin H, but for which the trivial name biotin has now become established. Biotin is present in the agents according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 0.001 to 0.01% by weight, in each case based on the entire application preparation.
Bevorzugt enthalten die erfindungsgemäßen Zweikomponentenmittel Vitamine, Provitamine und Vitaminvorstufen aus den Gruppen A, B, C, E und H.The two-component agents according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, C, E and H.
Panthenol, Pantolacton, Pyridoxin und seine Derivate sowie Nicotinsäureamid und Biotin sind besonders bevorzugt.Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinamide and biotin are particularly preferred.
Im Rahmen einer fünften bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zweikomponentenmittel mindestens einen Pflanzenextrakt.In a fifth preferred embodiment, the two-component agents according to the invention contain at least one plant extract.
Üblicherweise werden diese Extrakte durch Extraktion der gesamten Pflanze hergestellt. Es kann aber in einzelnen Fällen auch bevorzugt sein, die Extrakte ausschließlich aus Blüten und/oder Blättern der Pflanze herzustellen.These extracts are usually produced by extracting the entire plant. In individual cases, however, it may also be preferred to produce the extracts exclusively from flowers and / or leaves of the plant.
Hinsichtlich der erfindungsgemäß bevorzugten Pflanzenextrakte wird insbesondere auf die Extrakte hingewiesen, die in der auf Seite 44 der 3. Auflage des Leitfadens zur Inhalts- Stoffdeklaration kosmetischer Mittel, herausgegeben vom Industrieverband Körperpflege- und Waschmittel e.V. (IKW), Frankfurt, beginnenden Tabelle aufgeführt sind.With regard to the plant extracts preferred according to the invention, reference is made in particular to the extracts which are described in the third edition of the guide to the contents on page 44 of the Declaration of substances for cosmetic products, published by the Industrieverband Körperpflege- und Waschmittel eV (IKW), Frankfurt, are listed in the table below.
Erfindungsgemäß sind vor allem die Extrakte aus Grünem Tee, Eichenrinde, Brennnessel, Hamamelis, Hopfen, Henna, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Rosskastanie, Sandelholz, Wacholder, Kokosnuss, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel bevorzugt.According to the invention, the extracts from green tea, oak bark, nettle, witch hazel, hops, henna, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime , Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, hake, coltsfoot, marshmallow, meristem, ginseng and ginger root preferred.
Besonders bevorzugt sind die Extrakte aus Grünern Tee, Eichenrinde, Brennnessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Lindenblüten, Mandel, Aloe Vera, Kokosnuss, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Wiesenschaumkraut, Quendel, Schafgarbe, Hauhechel, Meristem, Ginseng und Ingwerwurzel.The extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, linden flowers, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, Rosemary, birch, cuckoo flower, quendel, yarrow, harrow, meristem, ginseng and ginger root.
Ganz besonders geeignet sind die Extrakte aus Grünem Tee, Mandel, Aloe Vera, Kokosnuss, Mango, Aprikose, Limone, Weizen, Kiwi und Melone.The extracts from green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi and melon are particularly suitable.
Als Extraktionsmittel zur Herstellung der genannten Pflanzenextrakte können Wasser, Alkohole sowie deren Mischungen verwendet werden. Unter den Alkoholen sind dabei niedere Alkohole wie Ethanol und Isopropanol, insbesondere aber mehrwertige Alkohole wie Ethylenglykol und Propylenglykol, sowohl als alleiniges Extraktionsmittel als auch in Mischung mit Wasser, bevorzugt. Pflanzenextrakte auf Basis von Wasser/Propylenglykol im Verhältnis 1:10 bis 10:1 haben sich als besonders geeignet erwiesen.Water, alcohols and mixtures thereof can be used as extractants for the production of the plant extracts mentioned. Among the alcohols, lower alcohols such as ethanol and isopropanol, but in particular polyhydric alcohols such as ethylene glycol and propylene glycol, are preferred, both as the sole extracting agent and as a mixture with water. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.
Die Pflanzenextrakte können erfindungsgemäß sowohl in reiner als auch in verdünnter Form eingesetzt werden. Sofern sie in verdünnter Form eingesetzt werden, enthalten sie üblicherweise ca. 2 - 80 Gew.-% Aktivsubstanz und als Lösungsmittel das bei ihrer Gewinnung eingesetzte Extraktionsmittel oder Extraktionsrnittelgemisch.According to the invention, the plant extracts can be used both in pure and in diluted form. If they are used in dilute form, they usually contain about 2 to 80% by weight of active substance and the extractant or extracting agent mixture used in their extraction as a solvent.
Weiterhin kann es bevorzugt sein, in den erfindungsgemäßen Mitteln Mischungen aus mehreren, insbesondere aus zwei, verschiedenen Pflanzenextrakten einzusetzen.Furthermore, it may be preferred to use mixtures of several, in particular two, different plant extracts in the agents according to the invention.
Im Rahmen einer sechsten Ausführungsform enthalten die erfindungsgemäßen Zweikomponentenmittel als Pflegestoff mindestens eine Carbonsäure. Vorteilhaft im Sinne der Erfindung können insbesondere kurzkettige Carbonsäuren sein. Unter kurzkettigen Carbonsäuren und deren Derivaten im Sinne der Erfindung werden Carbonsäuren verstanden, welche gesättigt oder ungesättigt und/oder geradkettig oder verzweigt oder cyclisch und/oder aromatisch und/oder heterocyclisch sein können und ein Molekulargewicht kleiner 750 aufweisen. Bevorzugt im Sinne der Erfindung können gesättigte oder ungesättigte geradkettigte oder verzweigte Carbonsäuren mit einer Kettenlänge von 1 bis zu 16 C-Atomen in der Kette sein, ganz besonders bevorzugt sind solche mit einer Kettenlänge von 1 bis zu 12 C - Atomen in der Kette.In a sixth embodiment, the two-component agents according to the invention contain at least one carboxylic acid as a care substance. Short-chain carboxylic acids can be particularly advantageous in the sense of the invention. Short-chain carboxylic acids and their derivatives for the purposes of the invention are understood to mean carboxylic acids which can be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and have a molecular weight of less than 750. For the purposes of the invention, preference may be given to saturated or unsaturated straight-chain or branched carboxylic acids with a chain length of 1 to 16 carbon atoms in the chain, very particularly preferred are those with a chain length of 1 to 12 carbon atoms in the chain.
Die kurzkettigen Carbonsäuren im Sinne der Erfindung können ein, zwei, drei oder mehr Carboxygruppen aufweisen. Bevorzugt im Sinne der Erfindung sind Carbonsäuren mit mehreren Carboxygruppen, insbesondere Di- und Tricarbonsäuren. Die Carboxygruppen können ganz oder teilweise als Ester, Säureanhydrid, Lacton, Amid, Imidsäure, Lactam, Lactim, Dicarboximid, Carbohydrazid, Hydrazon, Hydroxam, Hydroxim, Amidin, Amidoxim, Nitril, Phosphon- oder Phosphatester vorliegen. Die erfindungsgemäß einsetzbaren Carbonsäuren können selbstverständlich entlang der Kohlenstoffkette oder des Ringgerüstes substituiert sein. Zu den Substituenten der erfindungsgemäß einsetzbaren Carbonsäuren sind beispielsweise zu zählen d-C-s-Alkyl-, C2-C8-Alkenyl-, Aryl-, Aralkyl- und Aralkenyl-, Hydroxymethyl-, C2-C8-Hydroxyalkyl-,C2-C8-Hydroxyalkenyl-, Aminomethyl-, C2-C8-Aminoalkyl-, Cyano-, Formyl-, Oxo-, Thioxo-, Hydroxy-, Mercapto-, Amino-, Carboxy- oder Iminogruppen. Bevorzugte Substituenten sind d-C8-Alkyl-, Hydroxymethyl-, Hydroxy-, Amino- und Carboxygruppen. Besonders bevorzugt sind Substituenten in α- Stellung. Ganz besonders bevorzugte Substituenten sind Hydroxy-, Alkoxy- und Aminogruppen, wobei die Aminofunktion gegebenenfalls durch Alkyl-, Aryl-, Aralkyl- und/oder Alkenylreste weiter substituiert sein kann. Weiterhin sind ebenfalls bevorzugte Carbonsäurederivate die Phosphon- und Phosphatester.The short-chain carboxylic acids in the context of the invention can have one, two, three or more carboxy groups. For the purposes of the invention, preference is given to carboxylic acids having several carboxy groups, in particular di- and tricarboxylic acids. The carboxy groups can be present in whole or in part as an ester, acid anhydride, lactone, amide, imidic acid, lactam, lactim, dicarboximide, carbohydrazide, hydrazone, hydroxam, hydroxime, amidine, amidoxime, nitrile, phosphonic or phosphate ester. The carboxylic acids which can be used according to the invention can of course be substituted along the carbon chain or the ring structure. The substituents of the carboxylic acids which can be used according to the invention include, for example, dCs-alkyl, C 2 -C 8 -alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C 2 -C 8 -hydroxyalkyl, C 2 -C 8- Hydroxyalkenyl, aminomethyl, C 2 -C 8 aminoalkyl, cyano, formyl, oxo, thioxo, hydroxy, mercapto, amino, carboxy or imino groups. Preferred substituents are dC 8 alkyl, hydroxymethyl, hydroxy, amino and carboxy groups. Substituents in the α position are particularly preferred. Very particularly preferred substituents are hydroxyl, alkoxy and amino groups, where the amino function can optionally be further substituted by alkyl, aryl, aralkyl and / or alkenyl radicals. Furthermore, preferred carboxylic acid derivatives are the phosphonic and phosphate esters.
Als Beispiele für erfindungsgemäß einsetzbare Carbonsäuren seien genannt Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Isobuttersäure, Valeriansäure, Isovalerian- säure, Pivalinsäure, Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Glycerinsäure, Glyoxylsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure, Propiolsäure, Crotonsäure, Isocrotonsäure, Elaidinsäure, Maleinsäure, Fumarsäure, Muconsäure, Citraconsäure, Mesaconsäure, Camphersäure, Benzoesäure, o,m,p- Phthalsäure, Naphthoesäure, Toluoylsäure, Hydratropasäure, Atropasäure, Zimtsäure, Isonicotinsäure, Nicotinsäure, Bicarbaminsäure, 4,4'-Dicyano-6,6'-binicotinsäure, 8- Carbamoyloctansäure, 1 ,2,4-Pentantricarbonsäure, 2-Pyrrolcarbonsäure, 1 ,2,4,6,7- Napthalinpentaessigsäure, Malonaldehydsäure, 4-Hydroxy-phthalamidsäure, 1- Pyrazolcarbonsäure, Gallussäure oder Propantricarbonsäure, eine Dicarbonsäure ausgewählt aus der Gruppe, die gebildet wird durch Verbindungen der allgemeinen Formel (N-l),Examples of carboxylic acids which can be used according to the invention include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, propionic acid, sorbic acid, azelaic acid Crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoyl acid, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, 4,4'-carbonic acid -6,6 ' -binicotinic acid, 8- Carbamoyloctanoic acid, 1, 2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1, 2,4,6,7-naphthalenepentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazole carboxylic acid, gallic acid or propane tricarboxylic acid, a dicarboxylic acid selected from the group consisting of is formed by compounds of the general formula (Nl),
Figure imgf000035_0001
Figure imgf000035_0001
(N-I) in der Z steht für eine lineare oder verzweigte Alkyl- oder Alkenylgruppe mit 4 bis 12 Kohlenstoffatomen, n für eine Zahl von 4 bis 12 sowie eine der beiden Gruppen X und Y für eine COOH-Gruppe und die andere für Wasserstoff oder einen Methyl- oder Ethylrest, Dicarbonsäuren der allgemeinen Formel (N-l), die zusätzlich noch 1 bis 3 Methyl- oder Ethylsubstituenten am Cyclohexenring tragen sowie Dicarbonsäuren, die aus den Dicarbonsäuren gemäß Formel (N-l) formal durch Anlagerung eines Moleküls Wasser an die Doppelbindung im Cyclohexenring entstehen.(NI) in the Z stands for a linear or branched alkyl or alkenyl group with 4 to 12 carbon atoms, n for a number from 4 to 12 and one of the two groups X and Y for a COOH group and the other for hydrogen or one Methyl or ethyl radical, dicarboxylic acids of the general formula (Nl) which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids which formally form from the dicarboxylic acids of the formula (Nl) by the addition of a molecule of water to the double bond in the cyclohexene ring ,
Dicarbonsäuren der Formel (N-l) sind in der Literatur bekannt. So ist beispielweise der US-Patentschrift 3,753,968 ein Herstellungsverfahren zu entnehmen.Dicarboxylic acids of the formula (N-1) are known in the literature. For example, a manufacturing method can be found in US Pat. No. 3,753,968.
Die Dicarbonsäuren der Formel (N-l) können beispielsweise durch Umsetzung von mehrfach ungesättigten Dicarbonsäuren mit ungesättigten Monocarbonsäuren in Form einer Diels-Alder-Cyclisierung hergestellt werden. Üblicherweise wird man von einer mehrfach ungesättigten Fettsäure als Dicarbonsäurekomponente ausgehen. Bevorzugt ist die aus natürlichen Fetten und Ölen zugängliche Linolsäure. Als Monocarbonsäurekomponente sind insbesondere Acrylsäure, aber auch z.B. Methacrylsäure und Crotonsäure bevorzugt. Üblicherweise entstehen bei Reaktionen nach Diels-Alder Isomerengemische, bei denen eine Komponente im Uberschuss vorliegt. Diese Isomerengemische können erfindungsgemäß ebenso wie die reinen Verbindungen eingesetzt werden. Erfindungsgemäß einsetzbar neben den bevorzugten Dicarbonsäuren gemäß Formel (N- I) sind auch solche Dicarbonsäuren, die sich von den Verbindungen gemäß Formel (N-l) durch 1 bis 3 Methyl- oder Ethyl-Substituenten am Cyclohexylring unterscheiden oder aus diesen Verbindungen formal durch Anlagerung von einem Molekül Wasser an die Doppelbindung des Cyclohexenrings gebildet werden.The dicarboxylic acids of the formula (NI) can be prepared, for example, by reacting polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder cyclization. A polyunsaturated fatty acid is usually used as the dicarboxylic acid component. The linoleic acid accessible from natural fats and oils is preferred. Acrylic acid, but also, for example, methacrylic acid and crotonic acid are particularly preferred as the monocarboxylic acid component. Diels-Alder reactions usually produce mixtures of isomers in which one component is in excess. According to the invention, these isomer mixtures can be used just like the pure compounds. In addition to the preferred dicarboxylic acids of the formula (N-I), those dicarboxylic acids which differ from the compounds of the formula (Nl) by 1 to 3 methyl or ethyl substituents on the cyclohexyl ring or formally by addition of one of these compounds can also be used according to the invention Molecule of water are formed on the double bond of the cyclohexene ring.
Als erfindungsgemäß besonders wirksam hat sich die Dicarbonsäure(-mischung) erwiesen, die durch Umsetzung von Linolsäure mit Acrylsäure entsteht. Es handelt sich dabei um eine Mischung aus 5- und 6-Carboxy-4-hexyl-2-cyclohexen-1-octansäure. Solche Verbindungen sind kommerziell unter den Bezeichnungen Westvaco Diaeid® 1550 und Westvaco Diaeid® 1595 (Hersteller: Westvaco) erhältlich.The dicarboxylic acid (mixture) which results from the reaction of linoleic acid with acrylic acid has proven to be particularly effective according to the invention. It is a mixture of 5- and 6-carboxy-4-hexyl-2-cyclohexen-1-octanoic acid. Such compounds are commercially available under the designations Westvaco Diacid 1550 Westvaco Diacid ® ® 1595 (manufacturer: Westvaco).
Neben den zuvor beispielhaft aufgeführten erfindungsgemäßen kurzkettigen Carbonsäuren selbst können auch deren physiologisch verträgliche Salze erfindungsgemäß eingesetzt werden. Beispiele für solche Salze sind die Alkali-, Erdalkali-, Zinksalze sowie Ammoniumsalze, worunter im Rahmen der vorliegenden Anmeldung auch die Mono-, Di- und Trimethyl-, -ethyl- und -hydroxyethyl-Ammoniumsalze zu verstehen sind. Ganz besonders bevorzugt können im Rahmen der Erfindung jedoch mit alkalisch reagierenden Aminosäuren, wie beispielsweise Arginin, Lysin, Ornithin und Histidin, neutralisierte Säuren eingesetzt werden. Weiterhin kann es aus Formulierungsgründen bevorzugt sein, die Carbonsäure aus den wasserlöslichen Vertretern, insbesondere den wasserlöslichen Salzen, auszuwählen.In addition to the short-chain carboxylic acids themselves according to the invention, which have been exemplified above, their physiologically tolerable salts can also be used according to the invention. Examples of such salts are the alkali, alkaline earth, zinc and ammonium salts, which in the context of the present application are also to be understood as the mono-, di- and trimethyl-, -ethyl- and -hydroxyethyl-ammonium salts. However, acids which are neutralized with alkaline reacting amino acids, such as, for example, arginine, lysine, ornithine and histidine, can very particularly preferably be used in the context of the invention. For formulation reasons, it may furthermore be preferred to select the carboxylic acid from the water-soluble representatives, in particular the water-soluble salts.
Weiterhin ist es erfindungsgemäß bevorzugt 2-Pyrrolidinon-5-carbonsäure und deren Derivate als Carbonsäure einzusetzen. Besonders bevorzugt sind ie Natrium-, Kalium-, Calcium-, Magnesium- oder Ammoniumsalze, bei denen das Ammoniumion neben Wasserstoff eine bis drei Cr bis C -Alkylgruppen trägt. Das Natriumsalz ist ganz besonders bevorzugt. Die eingesetzten Mengen in den erfindungsgemäßen Mitteln betragen vorzugsweise 0,05 bis 10 Gew.%, bezogen auf die gesamte Anwendungszubereitung, besonders bevorzugt 0,1 bis 5 Gew.%, und insbesondere bevorzugt 0,1 bis 3 Gew.%.Furthermore, it is preferred according to the invention to use 2-pyrrolidinone-5-carboxylic acid and its derivatives as the carboxylic acid. Sodium, potassium, calcium, magnesium or ammonium salts are particularly preferred, in which the ammonium ion carries one to three Cr to C alkyl groups in addition to hydrogen. The sodium salt is very particularly preferred. The amounts used in the agents according to the invention are preferably 0.05 to 10% by weight, based on the entire application preparation, particularly preferably 0.1 to 5% by weight, and particularly preferably 0.1 to 3% by weight.
Weiterhin ist es erfindungsgemäß bevorzugt, Hydroxycarbonsäuren und hierbei wiederum insbesondere die Dihydroxy-, Trihydroxy- und Polyhydroxycarbonsäuren sowie die Dihy- droxy-, Trihydroxy- und Polyhydroxy- di-, tri- und polycarbonsäuren einzusetzen. Hierbei hat sich gezeigt, dass neben den Hydroxycarbonsäuren auch die Hydroxycarbonsäure- ester sowie die Mischungen aus Hydroxycarbonsäuren und deren Estern als auch polymere Hydroxycarbonsäuren und deren Ester ganz besonders bevorzugt sein können. Bevorzugte Hydroxycarbonsäureester sind beispielsweise Vollester der Glycolsäure, Milchsäure, Äpfelsäure, Weinsäure oder Citronensäure. Weitere grundsätzlich geeigneten Hydroxycarbonsäureester sind Ester der ß-Hydroxypropionsäure, der Tartronsäure, der D-Gluconsäure, der Zuckersäure, der Schleimsäure oder der Glucuronsäure. Als Alkoholkomponente dieser Ester eignen sich primäre, lineare oder verzweigte aliphatische Alkohole mit 8 - 22 C-Atomen, also z.B. Fettalkohole oder synthetische Fettalkohole. Dabei sind die Ester von d2-C15-Fettalkoholen besonders bevorzugt. Ester dieses Typs sind im Handel erhältlich, z.B. unter dem Warenzeichen Cosmacol® der EniChem, Augusta Industriale. Besonders bevorzugte Polyhydroxypolycarbonsäuren sind Polymilchsäure und Polyweinsäure sowie deren Ester.Furthermore, it is preferred according to the invention to use hydroxycarboxylic acids and in particular the dihydroxy, trihydroxy and polyhydroxycarboxylic acids as well as the dihydroxy, trihydroxy and polyhydroxydi, tri and polycarboxylic acids. It has been shown here that in addition to the hydroxycarboxylic acids, the hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters as well as polymeric hydroxycarboxylic acids and their esters can be very particularly preferred. Preferred hydroxycarboxylic acid esters are, for example, full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Other basically suitable hydroxycarboxylic acid esters are esters of β-hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid. Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols with 8-22 C atoms, for example fatty alcohols or synthetic fatty alcohols. The esters of d 2 -C 15 fatty alcohols are particularly preferred. Esters of this type are commercially available, eg under the trademark Cosmacol® ® EniChem, Augusta Industriale. Particularly preferred polyhydroxy polycarboxylic acids are polylactic acid and poly-tartaric acid and their esters.
Im Rahmen einer siebten bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zweikomponentenmittel als Pflegestoff mindestens ein Proteinhydrolysat und/oder eines seiner Derivate.In a seventh preferred embodiment, the two-component agents according to the invention contain at least one protein hydrolyzate and / or one of its derivatives as a care substance.
Proteinhydrolysate sind Produktgemische, die durch sauer, basisch oder enzymatisch katalysierten Abbau von Proteinen (Eiweißen) erhalten werden. Unter dem Begriff Proteinhydrolysate werden erfindungsgemäß auch Totalhydrolysate sowie einzelne Aminosäuren und deren Derivate sowie Gemische aus verschiedenen Aminosäuren verstanden. Weiterhin werden erfindungsgemäß aus Aminosäuren und Aminosäurederivaten aufgebaute Polymere unter dem Begriff Proteinhydrolysate verstanden. Zu letzteren sind beispielsweise Polyalanin, Polyasparagin, Polyserin etc. zu zählen. Weitere Beispiele für erfindungsgemäß einsetzbare Verbindungen sind L-Alanyl-L-prolin, Polyglycin, Glycyl-L- glutamin oder D/L-Methionin-S-Methylsulfoniumchlorid. Selbstverständlich können erfindungsgemäß auch ß-Aminosäuren und deren Derivate wie ß-Alanin, Anthranilsäure oder Hippursäure eingesetzt werden. Das Molgewicht der erfindungsgemäß einsetzbaren Proteinhydrolysate liegt zwischen 75, dem Molgewicht für Glycin, und 200.000, bevorzugt beträgt das Molgewicht 75 bis 50.000 und ganz besonders bevorzugt 75 bis 20.000 Dalton.Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins). According to the invention, the term protein hydrolyzates is also understood to mean total hydrolyzates and individual amino acids and their derivatives as well as mixtures of different amino acids. According to the invention, polymers constructed from amino acids and amino acid derivatives are furthermore to be understood under the term protein hydrolyzates. The latter include, for example, polyalanine, polyasparagine, polyserine, etc. Further examples of compounds which can be used according to the invention are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D / L-methionine-S-methylsulfonium chloride. Of course, ß-amino acids and their derivatives such as ß-alanine, anthranilic acid or hippuric acid can also be used according to the invention. The molecular weight of the protein hydrolyzates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and very particularly preferably 75 to 20,000 daltons.
Erfindungsgemäß können Proteinhydrolysate sowohl pflanzlichen als auch tierischen oder marinen oder synthetischen Ursprungs eingesetzt werden. Tierische Proteinhydrolysate sind beispielsweise Elastin-, Kollagen-, Keratin-, Seiden- und Milcheiweiß-Proteinhydrolysate, die auch in Form von Salzen vorliegen können. Solche Produkte werden beispielsweise unter den Warenzeichen Dehylan® (Cognis), Promois® (Interorgana), Collapuron® (Cognis), Nutrilan® (Cognis), Gelita-Sol® (Deutsche Gelatine Fabriken Stoess & Co), Lexein® (Inolex), Sericin (Pentapharm) und Kerasol® (Croda) vertrieben.According to the invention, protein hydrolyzates of plant, animal, marine or synthetic origin can be used. Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts. Such products are, for example, under the trademarks Dehylan ® (Cognis), Promois ® (Interorgana), Collapuron ® (Cognis), Nutrilan ® (Cognis), Gelita-Sol ® (Deutsche Gelatine Fabriken Stoess & Co), Lexein ® (Inolex), Sericin (Pentapharm) and Kerasol ® (Croda) sold.
Besonders interessant ist der Einsatz von Seiden-Proteinhydrolysaten. Unter Seide versteht man die Fasern des Kokons des Maulbeer-Seidenspinners (Bombyx mori L.). Die Rohseidenfaser besteht aus einem Doppelfaden Fibroin. Als Kittsubstanz hält Sericin diesen Doppelfaden zusammen. Seide besteht zu 70 - 80 Gew.% aus Fibroin, 19 - 28 Gew.% Sericin, 0,5 - 1 Gew.% aus Fett und 0,5 - 1 Gew.% aus Farbstoffen und mineralischen Bestandteilen.The use of silk protein hydrolyzates is particularly interesting. Silk is the fibers of the cocoon of the mulberry silk spinner (Bombyx mori L.). The raw silk fiber consists of a double thread of fibroin. As a cement substance, Sericin holds this double thread together. Silk consists of 70 - 80% by weight of fibroin, 19 - 28% by weight of sericin, 0.5 - 1% by weight of fat and 0.5 - 1% by weight of dyes and mineral components.
Die wesentlichen Bestandteile des Sericin sind mit ca. 46 Gew.% Hydroxyaminosäuren. Das Sericin besteht aus einer Gruppe von 5 bis 6 Proteinen. Die wesentlichen Aminosäuren des Sericines sind Serin (Ser, 37 Gew.%), Aspartat (Asp, 26 Gew.%), Glycin (Gly, 17 Gew.%), Alanin (Ala), Leucin (Leu) und Tyrosin (Tyr).The essential components of the Sericin are with approx. 46% by weight hydroxy amino acids. The sericin consists of a group of 5 to 6 proteins. The essential amino acids of the Sericines are serine (Ser, 37% by weight), aspartate (Asp, 26% by weight), glycine (Gly, 17% by weight), alanine (Ala), leucine (Leu) and tyrosine (Tyr) ,
Das wasserunlösliche Fibroin ist zu den Skieroproteinen mit langkettiger Molekülstruktur zu zählen. Die Hauptbestandteile des Fibroin sind Glycin (44 Gew.%), Alanin (26 Gew.%), und Tyrosin (13 Gew.%). Ein weiteres wesentliches Strukturmerkmal des Fibroins ist die Hexapeptidsequenz Ser-Gly-Ala-Gly-Ala-Gly.The water-insoluble fibroin is one of the skieroproteins with a long-chain molecular structure. The main components of fibroin are glycine (44% by weight), alanine (26% by weight), and tyrosine (13% by weight). Another essential structural feature of fibroin is the hexapeptide sequence Ser-Gly-Ala-Gly-Ala-Gly.
Technisch ist es auf einfache Art und Weise möglich, die beiden Seidenproteine voneinander zu trennen. So verwundert es nicht, dass sowohl Sericin als auch Fibroin als Rohstoffe zur Verwendung in kosmetischen Produkten jeweils für sich allein bekannt sind. Weiterhin sind Proteinhydrolysate und -derivate auf der Basis der jeweils einzelnen Seidenproteine bekannte Rohstoffe in kosmetischen Mitteln. So wird beispielsweise Sericin als solches seitens der Fa. Pentapharm Ltd. als Handels produkt mit der Bezeichnung Sericin Code 303-02 vertrieben. Weitaus häufiger noch wird Fibroin als Proteinhydrolysat mit unterschiedlichen Molekulargewichten im Markt angeboten. Diese Hydrolysate werden insbesondere als "Seidenhydroylsate" vertrieben. So wird beispielsweise unter der Handelsbezeichnung Promois® Silk hydrolysiertes Fibroin mit mittleren Molekulargewichten zwischen 350 und 1000 vertrieben. Auch in der DE 31 39 438 A1 werden kolloidale Fibroinlösungen als Zusatz in kosmetischen Mitteln beschrieben.Technically, it is possible to separate the two silk proteins from one another in a simple manner. It is therefore not surprising that both sericin and fibroin are known as raw materials for use in cosmetic products. Protein hydrolyzates and derivatives based on the individual silk proteins are also known raw materials in cosmetic products. For example, Sericin is used as such by Pentapharm Ltd. sold as a commercial product with the designation Sericin Code 303-02. Even more frequently, fibroin is offered on the market as a protein hydrolyzate with different molecular weights. These hydrolyzates are marketed in particular as "silk hydroylsates". For example, hydrolyzed fibroin with average molecular weights between 350 and 1000 is sold under the trade name Promois ® Silk. Also in DE 31 39 438 A1 describes colloidal fibroin solutions as an additive in cosmetic products.
Die positiven Eigenschaften der Seidenproteinderivate aus Sericin und Fibroin sind jeweils für sich genommen in der Literatur bekannt. So beschreibt die Verkaufsbroschüre der Fa. Pentapharm die kosmetischen Effekte des Sericines auf der Haut als reizlindernd, hydratisierend und filmbildend. Die Wirkung eines Fibroinderivates wird beispielsweise in der DE 31 39 438 A1 als pflegend und avivierend für das Haar beschrieben. Gemäß DE 102 40 757 A1 lässt sich bei einer gleichzeitigen Verwendung von Sericin und Fibroin bzw. deren Derivaten und/oder Hydrolysaten darüber hinaus eine synergistische Steigerung der positiven Wirkungen der Seidenproteine und deren Derivate erzielen.The positive properties of the silk protein derivatives from sericin and fibroin are known per se in the literature. The Pentapharm sales brochure describes the cosmetic effects of Sericine on the skin as soothing, hydrating and film-forming. The effect of a fibroin derivative is described, for example, in DE 31 39 438 A1 as nourishing and nourishing for the hair. According to DE 102 40 757 A1, when sericin and fibroin or their derivatives and / or hydrolyzates are used simultaneously, a synergistic increase in the positive effects of the silk proteins and their derivatives can also be achieved.
Bevorzugt wird daher im erfindungsgemäßen Zweikomponentenmittel als Seiden- Proteinhydrolysat ein Wirkstoffkomplex (A) bestehend aus dem Wirkstoff (A1 ) ausgewählt aus Sericin, Sericinhydrolysaten und/oder deren Derivaten, sowie Mischungen hieraus, und einem Wirkstoff (A2) ausgewählt aus Fibroin, und/oder Fibroinhydrolysaten und/oder deren Derivaten und/oder Mischungen hieraus eingesetzt.An active substance complex (A) consisting of the active substance (A1) selected from sericin, sericin hydrolyzates and / or their derivatives, and mixtures thereof, and an active substance (A2) selected from fibroin, and / or is therefore preferred in the two-component agent according to the invention as the silk protein hydrolyzate Fibroin hydrolyzates and / or their derivatives and / or mixtures thereof are used.
Der erfindungsgemäß verwendete Wirkstoffkomplex (A) verbessert signifikant in synergistischer Weise die zuvor dargestellten wesentlichen inneren und äußeren Strukturmerkmale und die Festigkeit sowie die Elastizität von menschlichen Haaren.The active ingredient complex (A) used according to the invention significantly, in a synergistic manner, improves the above-described essential internal and external structural features and the strength and elasticity of human hair.
Als Wirkstoffe (A1) können im Wirkstoffkomplex (A) verwendet werden:The following can be used as active ingredients (A1) in the active ingredient complex (A):
- natives Sericin,- native sericin,
- hydrolysiertes und/oder weiter derivatisiertes Sericin, wie beispielsweise Handelsprodukte mit den INCI - Bezeichnungen Sericin, Hydrolyzed Sericin, oder Hydrolyzed Silk,hydrolyzed and / or further derivatized sericin, such as commercial products with the INCI names Sericin, Hydrolyzed Sericin, or Hydrolyzed Silk,
- eine Mischung aus den Aminosäuren Serin, Aspartat und Glycin und/oder deren Methyl-, Propyl-, iso-Propyl-, Butyl-, iso-Butylestern, deren Salze wie beispielsweise Hydrochloride, Sulfate, Acetate, Citrate, Tartrate , wobei in dieser Mischung das Serin und/oder dessen Derivate zu 20 bis 60 Gew.%, das Aspartat und/oder dessen Derivate zu 10 - 40 Gew.% und das Glycin und/oder dessen Derivate zu 5 bis 30 Gew.% enthalten sind, mit der Maßgabe, dass sich die Mengen dieser Aminosäuren und/oder deren Derivate vorzugsweise zu 100 Gew.% ergänzen,- A mixture of the amino acids serine, aspartate and glycine and / or their methyl, propyl, iso-propyl, butyl, iso-butyl esters, their salts such as hydrochloride, sulfates, acetates, citrates, tartrates, in which Mixture containing 20 to 60% by weight of the serine and / or its derivatives, 10 to 40% by weight of the aspartate and / or its derivatives and 5 to 30% by weight of the glycine and / or its derivatives with which Provided that the amounts of these amino acids and / or their derivatives preferably add up to 100% by weight,
- sowie deren Mischungen. Als Wirkstoffe (A2) können im Wirkstoffkomplex (A) verwendet werden:- and their mixtures. The following can be used as active ingredients (A2) in the active ingredient complex (A):
- natives, in eine lösliche Form überführtes Fibroin,- native fibroin converted to a soluble form,
- hydrolysiertes und/oder weiter derivatisiertes Fibroin, besonders teilhydrolisiertes Fibroin, welches als Hauptbestandteil die Aminosäuresequenz Ser-Gly-Ala-Gly-Ala- Gly enthält,hydrolyzed and / or further derivatized fibroin, especially partially hydrolyzed fibroin, which contains the amino acid sequence Ser-Gly-Ala-Gly-Ala- Gly as the main component,
- die Aminosäuresequenz Ser-Gly-Ala-Gly-Ala-Gly,the amino acid sequence Ser-Gly-Ala-Gly-Ala-Gly,
- eine Mischung der Aminosäuren Glycin, Alanin und Tyrosin und/oder deren Methyl-, Propyl-, iso-Propyl-, Butyl-, iso-Butylestern, deren Salze wie beispielsweise Hydrochloride, Sulfate, Acetate, Citrate, Tartrate , wobei in dieser Mischung das Glycin und/oder dessen Derivate in Mengen von 20 - 60 Gew.%, das Alanin und dessen Derivate in Mengen von 10 - 40 Gew,% und das Tyrosin und dessen Derivate in Mengen von 0 bis 25 Gew.% enthalten sind, mit der Maßgabe, dass sich die Mengen dieser Aminosäuren und/oder deren Derivate vorzugsweise zu 100 Gew.% ergänzen, sowie deren Mischungen.- A mixture of the amino acids glycine, alanine and tyrosine and / or their methyl, propyl, iso-propyl, butyl, iso-butyl esters, their salts such as hydrochloride, sulfates, acetates, citrates, tartrates, in which mixture the glycine and / or its derivatives in amounts of 20-60% by weight, the alanine and its derivatives in amounts of 10-40% by weight and the tyrosine and its derivatives in amounts of 0 to 25% by weight are included provided that the amounts of these amino acids and / or their derivatives preferably add up to 100% by weight, as well as their mixtures.
Besonders gute pflegende Eigenschaften können erzielt werden, wenn eine der beiden Wirkstoffkomponenten des Wirkstoffkomplexes (A) in der nativen oder allenfalls löslich gemachten Form verwendet wird. Es ist auch möglich, eine Mischung aus mehreren Wirkstoffen (A1 ) und/oder (A2) einzusetzen.Particularly good care properties can be achieved if one of the two active ingredient components of the active ingredient complex (A) is used in the native or at most solubilized form. It is also possible to use a mixture of several active ingredients (A1) and / or (A2).
Es kann bevorzugt sein, dass die beiden Wirkstoffe (A1) und (A2) im Verhältnis von 10:90 bis 70:30, insbesondere 15:85 bis 50:50 und ganz besonders 20:80 bis 40:60 bezogen auf deren jeweilige Gehalte an aktiver Wirksubstanz in den erfindungsgemäßen Zweikomponentenmitteln eingesetzt werden.It may be preferred that the two active ingredients (A1) and (A2) in a ratio of 10:90 to 70:30, in particular 15:85 to 50:50 and very particularly 20:80 to 40:60, based on their respective contents of active ingredient in the two-component agents according to the invention.
Die Derivate der Hydrolysate von Sericin und Fibroin umfassen sowohl anionische als auch kationisierte Proteinhydrolysate. Die Proteinhydrolysate von Sericin und Fibroin sowie die daraus hergestellten Derivate können aus den entsprechenden Proteinen durch eine chemische, insbesondere alkalische oder saure Hydrolyse, durch eine enzymatische Hydrolyse und/oder einer Kombination aus beiden Hydrolysearten gewonnen werden. Die Hydrolyse von Proteinen ergibt in der Regel ein Proteinhydrolysat mit einer Molekulargewichtsverteilung von etwa 100 Dalton bis hin zu mehreren tausend Dalton. Bevorzugt sind solche Proteinhydrolysate von Sericin und Fibroin und/oder deren Derivate, deren zugrunde liegender Proteinanteil ein Molekulargewicht von 100 bis zu 250O0 Dalton, bevorzugt 250 bis 10000 Dalton aufweist. Weiterhin sind unter kationischen Proteinhydrolysaten von Sericin und Fibroin auch quaternierte Aminosäuren und deren Gemische zu verstehen. Die Quaternisierung der Proteinhydrolysate oder der Aminosäuren wird häufig mittels quartärer Ammoniumsalze wie beispielsweise N,N-Dime- thyl-N-(n-Alkyl)-N-(2-hydroxy-3-chloro-n-propyl)-ammoniumhalogeniden durchgeführt. Weiterhin können die kationischen Proteinhydrolysate auch noch weiter derivatisiert sein. Als typische Beispiele für die erfindungsgemäß einsetzbaren kationischen Proteinhydrolysate und -derivate seien die unter den INCI - Bezeichnungen im "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17th Street, N.W., Suite 300, Washington, DC 20036-4702) genannten und im Handel erhältlichen Produkte genannt: Cocodimonium Hydroxypropyl Hydrolyzed Silk, Cocodimonium Hydroxypropyl Silk Amino Acids, Hydroxyproypltrimonium Hydrolyzed Silk, Lauryldimonium Hydroxypropyl Hydrolyzed Silk, Steardimonium Hydroxypropyl Hydrolyzed Silk, Quatemiurn-79 Hydrolyzed Silk. Als typische Beispiele für die erfindungsgemäßen anionischen Proteinhydrolysate und -derivate seien die unter den INCI - Bezeichnungen im "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17th Street, N.W., Suite 300, Washington, DC 20036-4702) genannten und im Handel erhältlichen Produkte genannt: Potassium Cocoyl Hydrolyzed Silk, Sodium Lauroyl Hydrolyzed Silk oder Sodium Stearoyl Hydrolyzed Silk. Letztlich seien noch als typische Beispiele für die erfindungsgemäß einsetzbaren Derivate aus Sericin und Fibroin die unter den INCI - Bezeichnungen im Handel erhältlichen Produkte genannt: Ethyl Ester of Hydrolyzed Silk und Hydrolyzed Silk PG-Propyl Methylsilanediol. Weiterhin erfindungsgemäß verwendbar, wenngleich nicht unbedingt bevorzugt sind die im Handel erhältlichen Produkte mit den INCI - Bezeichnungen Palmitoyl Oligopeptide, Palmitoyl Pentapeptide-3, Palmitoyl Pentapeptide- 2, Acetyl Hexapeptide-1 , Acetyl Hexapeptide-3, Copper Tripeptide-1 , Hexapeptide-1 , Hexapeptide-2, MEA-Hydrolyzed Silk.The derivatives of the hydrolysates of sericin and fibroin include both anionic and cationized protein hydrolyzates. The protein hydrolysates of sericin and fibroin and the derivatives produced therefrom can be obtained from the corresponding proteins by chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate with a molecular weight distribution of approximately 100 daltons up to several thousand daltons. Preferred protein hydrolyzates of sericin and fibroin and / or their derivatives, the underlying protein portion of which has a molecular weight of 100 to 250,000 daltons, preferably 250 to 10,000 daltons. Furthermore, are under cationic Protein hydrolyzates of sericin and fibroin also understand quaternized amino acids and their mixtures. The quaternization of the protein hydrolyzates or the amino acids is often carried out using quaternary ammonium salts such as, for example, N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolyzates can also be further derivatized. As typical examples of the inventively employable cationic protein hydrolysates and derivatives are under the INCI - names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 th Street, NW, Suite 300, Washington, DC 20036-4702) and commercially available products: Cocodimonium Hydroxypropyl Hydrolyzed Silk, Cocodimonium Hydroxypropyl Silk Amino Acids, Hydroxyproypltrimonium Hydrolyzed Silk, Lauryldimonium Hydroxypropyl Hydrolyzed Silk, Steardimonium Hydroxypropyl Hydrolyzed Silk, Quatemiurn-79 Hydrolyzed Silk. Typical examples of the anionic protein hydrolyzates and derivatives according to the invention are those under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 th Street, NW, Suite 300 , Washington, DC 20036-4702) and commercially available products: Potassium Cocoyl Hydrolyzed Silk, Sodium Lauroyl Hydrolyzed Silk or Sodium Stearoyl Hydrolyzed Silk. Finally, typical examples of the derivatives of sericin and fibroin which can be used according to the invention are the products commercially available under the INCI names: ethyl ester of hydrolyzed silk and hydrolyzed silk PG-propyl methylsilanediol. Also usable according to the invention, although not necessarily preferred, are the commercially available products with the INCI names Palmitoyl Oligopeptide, Palmitoyl Pentapeptide-3, Palmitoyl Pentapeptide-2, Acetyl Hexapeptide-1, Acetyl Hexapeptide-3, Copper Tripeptide-1, Hexapeptide-1 , Hexapeptide-2, MEA-Hydrolyzed Silk.
Die Wirkung des erfindungsgemäßen Wirkstoffkomplexes (A) kann durch die Zugabe von Fettstoffen weiter gesteigert werden. Unter Fettstoffen sind zu verstehen Fettsäuren, Fettalkohole, natürliche und synthetische Wachse, welche sowohl in fester Form als auch flüssig in wässriger Dispersion vorliegen können, und natürliche und synthetische kosmetische Ölkomponenten zu verstehen.The effect of the active ingredient complex (A) according to the invention can be further increased by adding fatty substances. Fat substances are to be understood as meaning fatty acids, fatty alcohols, natural and synthetic waxes, which can be present both in solid form and in liquid form in aqueous dispersion, and natural and synthetic cosmetic oil components.
Erfindungsgemäß bevorzugt ist die Verwendung von Proteinhydrolysaten pflanzlichen Ursprungs, z. B. Soja-, Mandel-, Erbsen-, Kartoffel- und Weizenproteinhydrolysate. Solche Produkte sind beispielsweise unter den Warenzeichen Giuadin® (Cognis), DiaMin® (Diamalt), Lexein® (Inolex), Hydrosoy® (Croda), Hydrolupin® (Croda), Hydrosesarne® (Croda), Hydrotritium® (Croda) und Crotein® (Croda) erhältlich.According to the invention, the use of protein hydrolysates of plant origin, e.g. B. soy, almond, pea, potato and wheat protein hydrolyzates. Such products are, for example, under the trademarks Giuadin ® (Cognis), DiaMin ® (Diamalt), Lexein ® (Inolex), Hydrosoy ® (Croda), Hydrolupin ® (Croda), Hydrosesarne ® (Croda), Hydrotritium ® (Croda) and Crotein ® (Croda) available.
Wenngleich der Einsatz der Proteinhydrolysate als solche bevorzugt ist, können an deren Stelle gegebenenfalls auch anderweitig erhaltene Aminosäuregemische eingesetzt werden. Ebenfalls möglich ist der Einsatz von Derivaten der Proteinhydrolysate, beispielsweise in Form ihrer Fettsäure-Kondensationsprodukte. Solche Produkte werden beispielsweise unter den Bezeichnungen Lamepon® (Cognis), Lexein® (Inolex), Crolastin® (Croda), Crosilk® (Croda) oder Crotein® (Croda) vertrieben.Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures obtained in some other way can optionally be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products. Such products are sold for example under the names Lamepon ® (Cognis), Lexein ® (Inolex), Crolastin ® (Croda), Crosilk ® (Croda) or Crotein ® (Croda).
Selbstverständlich umfasst die erfindungsgemäße Lehre alle isomeren Formen, wie eis - trans - Isomere, Diastereomere und chirale Isomere.Of course, the teaching according to the invention encompasses all isomeric forms, such as ice-trans isomers, diastereomers and chiral isomers.
Erfindungsgemäß ist es auch möglich, eine Mischung aus mehreren Proteinhydrolysaten einzusetzen.According to the invention, it is also possible to use a mixture of several protein hydrolyzates.
Die Proteinhydrolysate sind in den erfindungsgemäßen Zweikomponentenmitteln beispielsweise in Konzentrationen von 0,01 Gew.% bis zu 20 Gew.%, vorzugsweise von 0,05 Gew.% bis zu 15 Gew.% und ganz besonders bevorzugt in Mengen von 0,05 Gew.% bis zu 5 Gew.%, jeweils bezogen auf die gesamte Anwendungszubereitung enthalten.The protein hydrolyzates in the two-component compositions according to the invention are, for example, in concentrations from 0.01% by weight to 20% by weight, preferably from 0.05% by weight to 15% by weight and very particularly preferably in amounts of 0.05% by weight. % up to 5% by weight, each based on the entire application preparation.
Im Rahmen einer achten bevorzugten Ausführungsform enthalten die erfindungsgemälien Zubereitungen als Pflegestoff Ectoin oder Ectoinderivate, Allantoin, Taurin und/oder Bisabolol.In an eighth preferred embodiment, the preparations according to the invention contain ectoin or ectoin derivatives, allantoin, taurine and / or bisabolol as a care substance.
Erfindungsgemäß werden unter dem Begriff "Ectoin und Ectoinderivate" Verbindungen der Formel (IV)According to the invention, compounds of the formula (IV) are used under the term “ectoin and ectoin derivatives”
Figure imgf000042_0001
und/oder deren physiologisch verträglichen Salzes und/oder einer isomeren oder stereoisomeren Form verstanden, wobei
Figure imgf000042_0001
and / or their physiologically compatible salt and / or an isomeric or stereoisomeric form, wherein
R10 steht für ein Wasserstoffatom, einen verzweigten oder unverzweigten d - C4-Alkylrest oder einen C2 - C4-Hydroxyalkylrest,R 10 represents a hydrogen atom, a branched or unbranched d - C 4 -alkyl radical or a C 2 - C 4 -hydroxyalkyl radical,
R11 steht für ein Wasserstoffatom, eine Gruppierung -CO OR14 oder eine Gruppierung - CO(NH)R14, wobei R 4 für ein Wasserstoffatom, einen d-, - C4-Alkylrest, einen Aminosäurerest, einen Dipeptid- oder einen Tripeptidrest stehen kann,R 11 stands for a hydrogen atom, a group -CO OR 14 or a group - CO (NH) R 14 , where R 4 stands for a hydrogen atom, a d-, - C 4 -alkyl radical, an amino acid radical, a dipeptide or a tripeptide radical can stand
R12 und R13 stehen unabhängig voneinander für ein Wasserstoffatom, einen d - C4- Alkylrest oder eine Hydroxygruppe mit der Maßgabe, dass nicht beide Reste gleichzeitig für eine Hydroxygruppe stehen dürfen, und n steht für eine ganze Zahl von 1 bis 3.R 12 and R 13 independently of one another represent a hydrogen atom, a d - C 4 alkyl radical or a hydroxyl group, with the proviso that both radicals may not simultaneously represent a hydroxyl group, and n represents an integer from 1 to 3.
Geeignete physiologisch verträgliche Salze der allgemeinen Verbindungen gemäß der Formel (IVa) oder (IVb) sind beispielsweise die Alkali-, Erdalkali-, Ammonium-, Triethylamin- oder Tris-(2-hydroxyethyl)aminsalze sowie solche, die sich aus der Umsetzung von Verbindungen gemäß der Formel (IVa) oder (IVb) mit anorganischen und organischen Säuren wie Salzsäure, Phosphorsäure, Schwefelsäure, verzweigten oder unverzweigten, substituierten oder unsubstituierten (beispielsweise durch eine oder mehrere Hydroxygruppen) C1 - C4- Mono- oder Dicarbonsäuren, aromatische Carbonsäuren und Sulfonsäuren wie Essigsäure, Citronensäure, Benzoesäure, Maleinsäure, Fumarsäure, Weinsäure und p-Toluolsulfonsäure ergeben. Beispiele für besonders bevorzugte physiologisch verträgliche Salze sind die Na-, K-, Mg- und Ca- und Ammoniumsalze der Verbindungen gemäß der Formel (IVa) oder (IVb), sowie die Salze, die sich durch Umsetzung von Verbindungen gemäß der Formel (IVa) oder (IVb) mit Salzsäure, Essigsäure, Citronensäure und Benzoesäure ergeben.Suitable physiologically tolerable salts of the general compounds of the formula (IVa) or (IVb) are, for example, the alkali, alkaline earth, ammonium, triethylamine or tris (2-hydroxyethyl) amine salts and those which result from the reaction of compounds according to the formula (IVa) or (IVb) with inorganic and organic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, branched or unbranched, substituted or unsubstituted (for example by one or more hydroxyl groups) C 1 - C 4 - mono- or dicarboxylic acids, aromatic carboxylic acids and sulfonic acids such as acetic acid, citric acid, benzoic acid, maleic acid, fumaric acid, tartaric acid and p-toluenesulfonic acid. Examples of particularly preferred physiologically compatible salts are the Na, K, Mg and Ca and ammonium salts of the compounds of the formula (IVa) or (IVb), and the salts which are formed by reacting compounds of the formula (IVa ) or (IVb) with hydrochloric acid, acetic acid, citric acid and benzoic acid.
Unter isomeren oder stereoisomeren Formen der Verbindungen gemäß Formel (IVa) oder (IVb) werden erfindungsgemäß alle auftretenden optischen Isomere, Diastereomere, Racemate, Zwitterionen, Kationen oder Gemische davon verstanden.According to the invention, isomeric or stereoisomeric forms of the compounds of the formula (IVa) or (IVb) are taken to mean all optical isomers, diastereomers, racemates, zwitterions, cations or mixtures thereof.
Unter dem Begriff Aminosäure werden die stereoisomeren Formen, z.B. D- und L- Formen, folgender Verbindungen verstanden:The term amino acid describes the stereoisomeric forms, e.g. D and L forms of the following compounds understood:
Asparagin, Arginin, Asparaginsäure, Glutamin, Glutaminsäure, ß-Alanin, γ-Aminobutyrat, Nε-Acetyllysin, Nδ-Acetylornitin, Nγ-Acetyldiaminobutyrat, Nα-Acetyldiaminobutyrat, Histidin, Isoleucin, Leucin, Methionin, Phenylalanin, Serin, Threonin und Tyrosin. L-Aminosäuren sind bevorzugt. Aminosäurereste leiten sich von den entsprechenden Aminosäuren ab. Die folgenden Aminosäurereste sind bevorzugt: Gly, Ala, Ser, Thr, Val, ß-Ala, γ-Aminobutyrat, Asp, Glu, Asn, Aln, Nε-Acetyllysin, Nδ- Acetylornithin, Nγ-Acetyldiaminobutyrat, Nα-Acetyldiaminobutyrat.Asparagine, arginine, aspartic acid, glutamine, glutamic acid, beta-alanine, γ-aminobutyrate, N ε -Acetyllysin, N δ -Acetylornitin, N γ -Acetyldiaminobutyrat, N α -Acetyldiaminobutyrat, histidine, isoleucine, leucine, methionine, phenylalanine, serine, Threonine and tyrosine. L-amino acids are preferred. Amino acid residues are derived from the corresponding amino acids. The following amino acid residues are preferred: Gly, Ala, Ser, Thr, Val, β-Ala, γ-aminobutyrate, Asp, Glu, Asn, Aln, N ε -acetyllysine, N δ - acetylornithine, N γ -acetyldiaminobutyrate, N α - Acetyldiaminobutyrat.
Die Kurzschreibweise der Aminosäuren erfolgte nach der allgemein üblichen Schreibweise. Die Di- oder Tripeptidreste sind in ihrer chemischen Natur nach Säureamide und zerfallen bei der Hydrolyse in 2 oder 3 Aminosäuren. Die Aminosäuren in dem Di- oder Tripeptidrest sind durch Amidbindungen miteinander verbunden.The shorthand notation of the amino acids was done according to the commonly used notation. In their chemical nature, the di- or tripeptide residues are acid amides and break down into 2 or 3 amino acids during hydrolysis. The amino acids in the di- or tripeptide residue are connected to one another by amide bonds.
Bezüglich der Herstellung der Di- und Tripeptidreste wird ausdrücklich auf die EP 0 671 161 A1 der Firma Marbert verwiesen. Auch Beispiele für Di- und Tripeptidreste sind der Offenbarung der EP 0 671 161 A1 zu entnehmen.With regard to the preparation of the di- and tripeptide residues, reference is expressly made to EP 0 671 161 A1 from Marbert. Examples of di- and tripeptide residues can also be found in the disclosure of EP 0 671 161 A1.
Beispiele für Ci - C4-Alkylgruppen in den erfindungsgemäßen Verbindungen sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl und tert.-Butyl. Bevorzugte Alkylgruppen sind Methyl und Ethyl, Methyl ist eine besonders bevorzugte Alkylgruppe. Bevorzugte C2 - C4- Hydroxyalkylgruppen sind die Gruppen 2-HydroxyethyI, 3-Hydroxypropyl oder 4-Hydroxy- butyl; 2-Hydroxyethyl ist eine besonders bevorzugte Hydroxyalkylgruppe.Examples of Ci - C 4 alkyl groups in the compounds according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Preferred alkyl groups are methyl and ethyl, methyl is a particularly preferred alkyl group. Preferred C 2 -C 4 -hydroxyalkyl groups are the groups 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; 2-Hydroxyethyl is a particularly preferred hydroxyalkyl group.
Die erfindungsgemäßen Zweikomponentenmittel enthalten diese Pflegestoffe bevorzugt in Mengen von 0,001 bis 2, insbesondere von 0,01 bis 0,5 Gew.-%, jeweils bezogen auf die gesamte Anwendungszubereitung.The two-component agents according to the invention preferably contain these care substances in amounts of 0.001 to 2, in particular 0.01 to 0.5% by weight, in each case based on the entire application preparation.
Im Rahmen einer neunten bevorzugten Ausführungsform enthält die Zubereitung (B) als Pflegestoff mindestens ein Mono- bzw. Oligosaccharid.In the context of a ninth preferred embodiment, the preparation (B) contains at least one mono- or oligosaccharide as a care substance.
Es können sowohl Monosaccharide als auch Oligosaccharide, wie beispielweise Rohrzucker, Milchzucker und Raffinose, eingesetzt werden. Die Verwendung von Mono- sacchariden ist erfindungsgemäß bevorzugt. Unter den Monosacchariden sind wiederum solche Verbindungen bevorzugt, die 5 oder 6 Kohlenstoffatome enthalten.Both monosaccharides and oligosaccharides, such as cane sugar, milk sugar and raffinose, can be used. The use of monosaccharides is preferred according to the invention. Among the monosaccharides, preference is again given to those compounds which contain 5 or 6 carbon atoms.
Geeignete Pentosen und Hexosen sind beispielsweise Ribose, Arabinose, Xylose, Lyxose, Allose, Altrose, Glucose, Mannose, Gulose, Idose, Galactose, Talose, Fucose und Fructose. Arabinose, Glucose, Galactose und Fructose sind bevorzugt eingesetzte Kohlenhydrate; Ganz besonders bevorzugt eingesetzt wird Glucose, die sowohl in der D- (+)- oder L-(-)- Konfiguration oder als Racemat geeignet ist.Suitable pentoses and hexoses are, for example, ribose, arabinose, xylose, lyxose, allose, old rose, glucose, mannose, gulose, idose, galactose, talose, fucose and fructose. Arabinose, glucose, galactose and fructose are preferred Carbohydrates; Glucose is very particularly preferably used, which is suitable both in the D- (+) - or L - (-) configuration or as a racemate.
Weiterhin können auch Derivate dieser Pentosen und Hexosen, wie die entsprechenden On- und Uronsäuren (Zuckersäuren), Zuckeralkohole und Glykoside, erfindungsgemäß eingesetzt werden. Bevorzugte Zuckersäuren sind die Gluconsäure, die Glucuronsäure, die Zuckersäure, die Mannozuckersäure und die Schleimsäure. Bevorzugte Zuckeralkohole sind Sorbit, Mannit und Duicit. Bevorzugte Glykoside sind die Methylglucoside.Derivatives of these pentoses and hexoses, such as the corresponding mono- and uronic acids (sugar acids), sugar alcohols and glycosides, can also be used according to the invention. Preferred sugar acids are gluconic acid, glucuronic acid, sugar acid, mannosugaric acid and mucic acid. Preferred sugar alcohols are sorbitol, mannitol and duicit. Preferred glycosides are the methyl glucosides.
Da die eingesetzten Mono- bzw. Oligosaccharide üblicherweise aus natürlichen Rohstoffen wie Stärke gewonnen werden, weisen sie in der Regel die diesen Rohstoffen entsprechenden Konfigurationen auf (z.B. D-Glucose, D-Fructose und D-Galactose).Since the mono- or oligosaccharides used are usually obtained from natural raw materials such as starch, they usually have the configurations corresponding to these raw materials (e.g. D-glucose, D-fructose and D-galactose).
Die Mono- bzw. Oligosaccharide sind in den erfindungsgemäßen Haarbehandlungsmitteln bevorzugt in einer Menge von 0,1 bis 8 Gew.-%, insbesondere bevorzugt 1 bis 5 Gew.-%, bezogen auf die gesamte Anwendungszubereitung, enthalten.The monosaccharides or oligosaccharides are preferably present in the hair treatment compositions according to the invention in an amount of 0.1 to 8% by weight, particularly preferably 1 to 5% by weight, based on the entire application preparation.
Im Rahmen einer zehnten Ausführungsform enthält das erfindungsgemäße Zweikomponentenmittel als Pflegestoff mindestens ein Silikonöl und/oder ein Silikongum.In a tenth embodiment, the two-component agent according to the invention contains at least one silicone oil and / or one silicone gum as a care substance.
Erfindungsgemäß geeignete Silikone oder Silikongums sind insbesondere Dialkyl- und Alkylarylsiloxane, wie beispielsweise Dimethylpolysiloxan und Methylphenyl-polysiloxan, sowie deren alkoxylierte, quaternierte oder auch anionische Derivate.Silicones or silicone gums suitable according to the invention are in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated, quaternized or also anionic derivatives.
Beispiele für solche Silikone sind: - Oligomere Polydimethylcyclosiloxane (INCI-Bezeichnung: Cyclomethicone), insbesondere die tetramere und die pentamere Verbindung, die als Handelsprodukte DC 344 bzw. DC 345 von Dow Corning vertrieben werden, - Hexamethyl-Disiloxan (INCI-Bezeichnung: Hexamethyldisiloxane), z. B. das unter der Bezeichnung Abil® K 520 vertriebenen Produkt, - Polymere Polydimethylsiloxane (INCI-Bezeichnung: Dimethicone), z. B. die unter der Bezeichnung DC 200 von Dow Corning vertriebenen Produkte, - Polyphenylmethylsiloxane (INCI-Bezeichnung: Phenyl Trimethicone), z. B. das Handelsprodukt DC 556 Fluid von Dow Corning, - Silicon-Glykol-Copolymere (INCI-Bezeichnung: Dimethicone Copolyol), z. B. die Handelsprodukte DC 190 und DC 193 von Dow Corning, - Ester sowie Partialester der Silicon-Glykol-Copolymere, wie sie beispielsweise von der Firma Fanning unter der Handelsbezeichnung Fancorsil® LIM (INCI- Bezeichnung: Dimethicone Copolyol Meadowfoamate) vertrieben werden, - Dimethylsiloxane mit Hydroxy-Endgruppen (INCI-Bezeichnung: Dimethiconol), z. B. die Handelsprodukte DC 1401 und Q2-1403 von Dow Corning, - aminofunktionelle Polydimethylsiloxane und hydroxylaminomodifizierte Silicone (INCI-Bezeichnung: u. a. Amodimethicone und Quaternium-80), wie die Handelsprodukte XF42-B1989 (Hersteller GE Toshiba Silicones) Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning® 939 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM- 55067 (Hersteller: Wacker) sowie Abil®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt), - anionische Silikonöle, wie beispielsweise das Produkt Dow Coming®1784 - aminomodifizierte Organosilicone, wie beispielsweise das Produkt Abil Soft A843 (Hersteller Osi Specialities).Examples of such silicones are: - Oligomeric polydimethylcyclosiloxanes (INCI name: Cyclomethicone), in particular the tetramer and the pentamer compound, which are sold as commercial products DC 344 and DC 345 by Dow Corning, - Hexamethyl-disiloxane (INCI name: Hexamethyldisiloxane ), e.g. B. the product sold under the name Abil ® K 520, - Polydimethylsiloxane (INCI name: Dimethicone), z. B. the products sold under the name DC 200 by Dow Corning, - Polyphenylmethylsiloxane (INCI name: Phenyl Trimethicone), z. B. the commercial product DC 556 Fluid from Dow Corning, - Silicon-glycol copolymers (INCI name: Dimethicone Copolyol), e.g. , The commercial products DC 190 and DC 193 from Dow Corning, - esters and partial esters of silicone glycol copolymers, such as, for example, by the company Fanning under the trade designation Fancorsil ® LIM (INCI name: dimethicone copolyol Meadowfoamate) are distributed, - Dimethylsiloxanes with hydroxy end groups (INCI name: Dimethiconol), e.g. B. the commercial products DC 1401 and Q2-1403 from Dow Corning, - amino-functional polydimethylsiloxanes and hydroxylamino-modified silicones (INCI name: inter alia amodimethicone and quaternium-80), such as the commercial products XF42-B1989 (manufacturer GE Toshiba Silicones) Q2-7224 (manufacturer : Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning ® 939 emulsion (containing a hydroxylamino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) as well as Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt), - anionic silicone oils, such as the product Dow Coming ® 1784 - amino-modified organosilicones, such as the product Abil Soft A843 (manufacturer Osi Specialties).
Gemäß einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zubereitungen eine Kombination aus einem flüchtigen und einem nichtflüchtigen Silikon. Flüchtig im Sinne der Erfindung sind solche Silikone, die ein Flüchtigkeit aufweisen, die gleich oder größer als die Flüchtigkeit des zyklischen, pentameren Dimethylsiloxans ist. Solche Kombinationen sind auch als Handelsprodukte (z. B. Dow Corning®1401, Dow Corning®1403 und Dow Corning®1501, jeweils Mischungen aus einem Cyclomethicone und einem Dimethiconol) erhältlich.According to a preferred embodiment, the preparations according to the invention contain a combination of a volatile and a non-volatile silicone. Volatile in the sense of the invention are those silicones which have a volatility which is equal to or greater than the volatility of the cyclic, pentameric dimethylsiloxane. Such combinations are also available as commercial products (eg Dow Corning® 1401, Dow Corning® 1403 and Dow Corning® 1501, in each case mixtures of a cyclomethicone and a dimethiconol).
Gemäß einer besonders bevorzugten Ausführungsform enthält die Zubereitung (B) als Pflegestoff ein Dialkylpolysiloxan oder eines seiner Derivate. Bevorzugt sind die Alkyl- gruppen Methyl, Ethyl, i-Propyl und n-Propyl. Dimethylpolysiloxan oder eines seiner Derivate wird besonders bevorzugt eingesetzt. Bevorzugte sind die Derivate des Dimethylpolysiloxans, die aminofunktionell sind. Ein ganz besonders bevorzugtes Derivat ist unter der INCI-Bezeichnung Amodimethicone im Handel erhältlich. Die erfindungsgemäßen Zubereitungen enthalten die Silikone bevorzugt in Mengen von 0,01 - 10 Gew.-%, insbesondere 0,1 - 5 Gew.-%, bezogen auf die gesamte Anwendungszubereitung.According to a particularly preferred embodiment, preparation (B) contains a dialkylpolysiloxane or one of its derivatives as a care substance. The alkyl groups are preferably methyl, ethyl, i-propyl and n-propyl. Dimethylpolysiloxane or one of its derivatives is particularly preferably used. The derivatives of dimethylpolysiloxane which are amino-functional are preferred. A very particularly preferred derivative is commercially available under the INCI name Amodimethicone. The preparations according to the invention preferably contain the silicones in amounts of 0.01-10% by weight, in particular 0.1-5% by weight, based on the entire application preparation.
Im Rahmen einer elften Ausführungsform enthält die Zubereitung (B) mindestens ein Lipid als Pflegestoff.In an eleventh embodiment, preparation (B) contains at least one lipid as a care substance.
Erfindungsgemäß geeignete Lipide sind Phospholipide, beispielsweise Sojalecithin, Ei- Lecithin und Kephaline sowie die unter den INCI-Bezeichnungen Linoleamidopropyl PG- Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate und Stearamidopropyl PG-Dimonium Chloride Phosphate bekannten Substanzen. Diese werden beispielsweise von der Firma Mona unter den Handelsbezeichnungen Phospholipid EFA®, Phospholipid PTC® sowie Phospholipid SV® vertrieben.Lipids suitable according to the invention are phospholipids, for example soy lecithin, egg lecithin and cephaline, and also the substances known under the INCI names linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate and Stearamidopropyl PG-Dimonium Chloride Phosphate. These are sold, for example, by Mona under the trade names Phospholipid EFA ® , Phospholipid PTC ® and Phospholipid SV ® .
Die erfindungsgemäßen Zubereitungen enthalten die Lipide bevorzugt in Mengen von 0,01 - 10 Gew.-%, insbesondere 0,1 - 5 Gew.-%, bezogen auf die gesamte Anwendungszubereitung.The preparations according to the invention preferably contain the lipids in amounts of 0.01-10% by weight, in particular 0.1-5% by weight, based on the entire application preparation.
Im Rahmen einer zwölften Ausführungsform enthält die Zubereitung (B) mindestens einen Ölkörper als Pflegestoff.In a twelfth embodiment, the preparation (B) contains at least one oil body as a care substance.
Zu den natürlichen und synthetischen kosmetischen Olkörpem sind beispielsweise zu zählen:The natural and synthetic cosmetic oil bodies include, for example:
- pflanzliche Öle. Beispiele für solche Öle sind Sonnenblumenöl, Olivenöl, Sojaöl, Rapsöl, Mandelöl, Jojobaöl, Orangenöl, Weizenkeimöl, Pfirsichkemöl und die flüssigen Anteile des Kokosöls. Geeignet sind aber auch andere Triglyceridöle wie die flüssigen Anteile des Rindertalgs sowie synthetische Triglyceridöle.- vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach seed oil and the liquid components of coconut oil. Other triglyceride oils such as the liquid portions of beef tallow and synthetic triglyceride oils are also suitable.
- flüssige Paraffinöle, Isoparaffinöle und synthetische Kohlenwasserstoffe sowie Di-n- alkylether mit insgesamt zwischen 12 bis 36 C-Atomen, insbesondere 12 bis 24 C- Atomen, wie beispielsweise Di-n-octylether, Di-n-decylether, Di-n-nonylether, Di-n- undecylether, Di-n-dodecylether, n-Hexyl-n-octylether, n-Octyl-n-decylether, n-Decyl- n-undecylether, n-Undecyl-n-dodecylether und n-Hexyl-n-Undecylether sowie Di-tert- butylether, Di-iso-pentylether, Di-3-ethyldecylether, tert.-Butyl-n-octylether, iso-Pentyl- n-octylether und 2-Methyl-pentyl-n-octylether. Die als Handelsprodukte erhältlichen Verbindungen 1,3-Di-(2-ethyl-hexyl)-cyclohexan (Cetiol® S) und Di-n-octylether (Cetiol®OE) können bevorzugt sein. Esteröle. Unter Esterölen sind zu verstehen die Ester von C6 - C30 - Fettsäuren mit C2 - C30 - Fettalkoholen. Bevorzugt sind die Monoester der Fettsäuren mit Alkoholen mit 2 bis 24 C-Atomen. Beispiele für eingesetzte Fettsäurenanteile in den Estern sind Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecan- säure, Myristinsäure, Palmitinsäure, Palmitoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, die z.B. bei der Druckspaltung von natürlichen Fetten und Ölen, bei der Oxidation von Aldehyden aus der Roelen'schen Oxosynthese oder der Dirnerisierung von ungesättigten Fettsäuren anfallen. Beispiele für die Fettalkoholantesile in den Esterölen sind Isopropylalkohol, Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elai dylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylal- kohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxosynthese sowie als Monomerfraktion bei der Dirnerisierung von ungesättigten Fettalkoholen anfallen. Erfindungsgemäß besonders bevorzugt sind Isopro pylmyristat (Rilanit® IPM), lsononansäure-C16-18-alkylester (Cetiol® SN), 2-Ethylhesχylpalmitat (Cegesoft® 24), Stearinsäure-2-ethylhexylester (Cetiol® 868), Cetyloleat, Gtycerintrica- prylat, Kokosfettalkohol-caprinat/-caprylat (Cetiol® LC), n-Butylstearat, Oleylerucat (Cetiol® J 600), Isopropylpalmitat (Rilanit® IPP), Oleyl Oleate (Cetiol®), Laurinsäure- hexylester (Cetiol® A), Di-n-butyladipat (Cetiol® B), Myristylmyristat (Cetiol® MM), Cetearyl Isononanoate (Cetiol® SN), Ölsäuredecylester (Cetiol® V). Dicarbonsäureester wie Di-n-butyladipat, Di-(2-ethylhexyl)-adipat, Di-(2-ethylhexyl)- succinat und Di-isotridecylacelaat sowie Diolester wie Ethylenglykol-dioleat, Ethylenglykol-di-isotridecanoat, Propylenglykol-di(2-ethylhexanoat), Propylenglykol-di- isostearat, Propylenglykol-di-pelargonat, Butandiol-di-isostearat, Neopentylglykol- dicaprylat, symmetrische, unsymmetrische oder cyclische Ester der Kohlensäure m it Fettalkoholen, beispielsweise beschrieben in der DE-OS 197 56 454, Glycerincarbonat oder Dicaprylylcarbonat (Cetiol® CC),- Liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n-octyl ether, di-n-decyl ether, di-n- nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl n-Undecyl ether and di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The compounds are available as commercial products 1,3-di- (2-ethyl-hexyl) -cyclohexane (Cetiol ® S), and di-n-octyl ether (Cetiol ® OE) may be preferred. Esteröle. Ester oils are understood to be the esters of C 6 -C 30 fatty acids with C 2 -C 30 fatty alcohols. The monoesters of fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid moieties in the esters are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, Isotridecan- acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, Behenic acid and erucic acid, as well as their technical mixtures, which occur, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or in the directing of unsaturated fatty acids. Examples of the fatty alcohol alcohol parts in the ester oils are isopropyl alcohol, capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaolyl alcohol, elaol alcohol, elaol alcohol, elaol alcohol , Gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the directing of unsaturated fatty alcohols. According to the invention particularly preferably isopropyl pylmyristat (Rilanit ® IPM), isononanoic acid C16-18 alkyl ester (Cetiol ® SN), 2-Ethylhes χ ylpalmitat (Cegesoft ® 24), stearic acid-2-ethylhexyl ester (Cetiol ® 868), cetyl oleate, Gtycerintrica - prylate, coconut fatty alcohol caprinate / caprylate (Cetiol ® LC), n-butyl stearate, olerlerucate (Cetiol ® J 600), isopropyl palmitate (Rilanit ® IPP), oleyl oleate (Cetiol ® ), lauric acid hexyl ester (Cetiol ® A), Di-n-butyl adipate (Cetiol ® B), myristyl myristate (Cetiol ® MM), cetearyl isononanoate (Cetiol ® SN), oleic acid decyl ester (Cetiol ® V). Dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecylacelate as well as diol esters such as ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di (2- ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate, neopentyl glycol dicaprylate, symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or Dicaprylyl carbonate (Cetiol ® CC),
Trifettsäureester von gesättigten und/oder ungesättigten linearen und/oder verzweigten Fettsäuren mit Glycerin, - Fettsäurepartialglyceride, worunter Monoglyceride, Diglyceride und deren technische Gemische zu verstehen sind. Bei der Verwendung technischer Produkte können herstellungsbedingt noch geringe Mengen Triglyceride enthalten sein. Die Partialglyceride folgen vorzugsweise der Formel (D4-I),Trifatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol, - Fatty acid partial glycerides, including monoglycerides, diglycerides and their technical mixtures. When using technical products, small quantities of triglycerides may still be present due to the manufacturing process. The partial glycerides preferably follow the formula (D4-I),
CH20(CH2CH20)mR1 I CHO(CH2CH20)nR2 (D4-I) I CH20(CH2CH20)qR3 in der R1, R2 und R3 unabhängig voneinander für Wasserstoff oder für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22, vorzugsweise 12 bis 18, Kohlenstoffatomen stehen mit der Maßgabe, dass mindestens eine dieser Gruppen für einen Acylrest und mindestens eine dieser Gruppen für Wasserstoff steht. Die Summe (m+n+q) steht für 0 oder Zahlen von 1 bis 100, vorzugsweise für 0 oder 5 bis 25. Bevorzugt steht R1 für einen Acylrest und R2 und R3 für Wasserstoff und die Summe (m+n+q) ist 0. Typische Beispiele sind Mono- und/oder Diglyceride auf Basis von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen. Vorzugsweise werden Ölsäuremonoglyceride eingesetzt.CH 2 0 (CH 2 CH 2 0) m R 1 I CHO (CH 2 CH 2 0) n R 2 (D4-I) I CH 2 0 (CH 2 CH 2 0) q R 3 in the R 1 , R 2 and R 3 independently of one another represent hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups is an acyl radical and at least one of these groups stands for hydrogen. The sum (m + n + q) represents 0 or numbers from 1 to 100, preferably 0 or 5 to 25. R 1 preferably represents an acyl radical and R 2 and R 3 represents hydrogen and the sum (m + n + q) is 0. Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linoleic acid , Elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Oleic acid monoglycerides are preferably used.
Die Einsatzmenge der natürlichen und synthetischen kosmetischen Ölkörper in den erfindungsgemäßen Zweikomponentenmitteln beträgt üblicherweise 0,1 - 30 Gew.%, bezogen auf die gesamte Anwendungszubereitung, bevorzugt 0,1 - 20 Gew.-%, und insbesondere 0,1 - 15 Gew.-%.The amount of natural and synthetic cosmetic oil bodies used in the two-component compositions according to the invention is usually 0.1-30% by weight, based on the overall application preparation, preferably 0.1-20% by weight, and in particular 0.1-15% by weight. %.
Im Rahmen einer dreizehnten Ausführungsform enthält die Zubereitung (B) ein Enzym als Pflegestoff. Erfindungsgemäß besonders bevorzugte Enzyme sind ausgewählt aus einer Gruppe, die gebildet wird aus Proteasen, Lipasen, Transglutaminase, Oxidasen und Peroxidasen. Im Rahmen einer vierzehnten Ausführungsform enthalten die erfindungsgemäßen Zweikomponentenmittel mindestens einen Perlenextrakt.In a thirteenth embodiment, preparation (B) contains an enzyme as a care substance. Enzymes which are particularly preferred according to the invention are selected from a group which is formed from proteases, lipases, transglutaminase, oxidases and peroxidases. In a fourteenth embodiment, the two-component agents according to the invention contain at least one pearl extract.
Perlen von Muscheln bestehen im wesentlichen aus anorganischen und organischen Calciumsalzen, Spurenelementen und Proteinen. Perlen lassen sich auf einfache Weise aus kultivierten Muscheln gewinnen. Die Kultivierung der Muscheln kann sowohl in Süßwasser als auch in Meereswasser erfolgen. Dies kann sich auf die Inhaltsstoffe der Perlen auswirken. Erfindungsgemäß bevorzugt ist ein Perlenextrakt, welcher von in Meeres- bzw. Salzwasser kultivierten Muscheln stammt. Die Perlen bestehen zu einem großen Teil aus Aragonit (Calciumcarbonat), Conchiolin und einem Albuminoid. Letztere Bestandteile sind Proteine. Weiterhin sind in Perlen noch Magnesium- und Natriumsalze, anorganische Siliciumverbindungen sowie Phosphate enthalten.Pearls of mussels consist essentially of inorganic and organic calcium salts, trace elements and proteins. Pearls can easily be obtained from cultivated shells. The mussels can be cultivated in both fresh water and sea water. This can affect the ingredients of the pearls. According to the invention, a pearl extract is preferred which comes from mussels cultivated in sea or salt water. The pearls consist largely of aragonite (calcium carbonate), conchiolin and an albuminoid. The latter components are proteins. Pearls also contain magnesium and sodium salts, inorganic silicon compounds and phosphates.
Zur Herstellung des Perlenextraktes werden die Perlen pulverisiert. Danach werden die pulverisierten Perlen mit den üblichen Methoden extrahiert. Als Extraktionsmittel zur Herstellung der Perlenextrakte können Wasser, Alkohole sowie deren Mischungen verwendet werden. Unter Wasser sind dabei sowohl demineralisiertes Wasser, als auch Meereswasser zu verstehen. Unter den Alkoholen sind dabei niedere Alkohole wie Ethanol und Isopropanol, insbesondere aber mehrwertige Alkohole wie Glycerin, Diglycerin, Triglycerin, Polyglycerin, Ethylenglykol, Propylenglykol und Butylenglykol, sowohl als alleiniges Extraktionsmittel als auch in Mischung mit demineralisiertem Wasser oder Meereswasser, bevorzugt. Perlenextrakte auf Basis von Wasser/Glyceringemischen haben sich als besonders geeignet erwiesen. Je nach Extraktionsbedingungen können die Perlenproteine (Conchiloin und Albuminoid) weitestgehend in nativem Zustand oder bereits teilweise oder weitestgehend als Proteinhydrolysate vorliegen. Bevorzugt ist ein Perlenextrakt, in welchem Conchiolin und Albuminoid bereits teilweise hydrolysiert vorliegen. Die wesentlichen Aminosäuren dieser Proteine sind Glutaminsäure, Serin, Alanin, Glycin, Asparaginsäure und Phenylalanin. In einer weiteren besonders bevorzugten Ausgestaltung kann es vorteilhaft sein, wenn der Perlenextrakt zusätzlich mit mindestens einer oder mehreren dieser Aminosäuren angereichert wird. In der bevorzugtesten Ausführungsform ist der Perlenextrakt angereichert mit Glutaminsäure, Serin und Leucin. Weiterhin findet sich je nach Extraktionsbedingungen, insbesondere in Abhängigkeit von der Wahl des Extraktionsmittels ein mehr oder weniger großer Anteil an Mineralien und Spurenelementen im Extrakt wieder. Ein bevorzugter Extrakt enthält organische und/oder anorganische Calciumsalze sowie Magnesium- und Natriumsalze, anorganische Siliciumverbindungen und/oder Phosphate. Ein ganz besonders bevorzugter Perlenextrakt enthält mindestens 75 %, bevorzugt 85 %, besonders bevorzugt 90 % und ganz besonders bevorzugt 95 % aller Inhaltsstoffe der natürlich vorkommenden Perlen. Beispiele für erfindungsgemäß einsetzbare Perlenextrakte sind die Handelsprodukte Pearl Protein Extract BG® oder Crodarom® Pearl.The pearls are pulverized to produce the pearl extract. The powdered beads are then extracted using the usual methods. Water, alcohols and mixtures thereof can be used as extractants for the preparation of the pearl extracts. Water is understood to mean both demineralized water and sea water. Among the alcohols, lower alcohols such as ethanol and isopropanol, but in particular polyhydric alcohols such as glycerol, diglycerol, triglycerol, polyglycerol, ethylene glycol, propylene glycol and butylene glycol, are preferred, both as the sole extracting agent and as a mixture with demineralized water or sea water. Pearl extracts based on water / glycerin mixtures have proven to be particularly suitable. Depending on the extraction conditions, the pearl proteins (conchiloin and albuminoid) can be largely in their native state or already partially or largely as protein hydrolyzates. A pearl extract in which the conchiolin and albuminoid are already partially hydrolyzed is preferred. The essential amino acids of these proteins are glutamic acid, serine, alanine, glycine, aspartic acid and phenylalanine. In a further particularly preferred embodiment, it can be advantageous if the pearl extract is additionally enriched with at least one or more of these amino acids. In the most preferred embodiment, the pearl extract is enriched with glutamic acid, serine and leucine. Furthermore, depending on the extraction conditions, in particular depending on the choice of extracting agent, a more or less large proportion of minerals and trace elements can be found in the extract. A preferred extract contains organic and / or inorganic calcium salts as well as magnesium and sodium salts, inorganic silicon compounds and / or phosphates. A very preferred pearl extract contains at least 75%, preferably 85%, particularly preferably 90% and very particularly preferably 95% of all ingredients of the naturally occurring pearls. Examples of pearl extracts usable according to the invention are the commercial products Pearl Protein Extract BG ® or Crodarom ® Pearl.
Die zuvor beschriebenen Perlenextrakte sind vorzugsweise in einer Menge von mindestens 0,01 bis zu 20 Gew.% enthalten. Bevorzugt werden Mengen des Extraktes von 0,01 bis zu 10 Gew.%, ganz besonders bevorzugt Mengen von 0,01 bis 5 Gew.% bezogen auf das gesamte Zweikomponentenmittel verwendet.The pearl extracts described above are preferably contained in an amount of at least 0.01 to 20% by weight. Amounts of the extract of 0.01 to 10% by weight are preferably used, very particularly preferably amounts of 0.01 to 5% by weight, based on the total two-component agent.
Obwohl jeder der in den verschiedenen Ausführungsformen genannten Pflegestoffe für sich alleine bereits ein zufriedenstellenden Resultat ergibt, sind im Rahmen der vorliegenden Erfindung auch alle Ausführungsformen umfasst, in denen die Zubereitung (B) mehrere Pflegestoffe auch aus verschiedenen Gruppen enthält.Although each of the care substances mentioned in the various embodiments already gives a satisfactory result on its own, the scope of the present invention also includes all embodiments in which the preparation (B) contains a plurality of care substances from different groups.
Das erfindungsgemäße Zweikomponentenmittel ist in verschiedenen Kammern einer Mehrkammertube konfektioniert. Vorzugsweise handelt es bei der Mehrkammertube um eine Zweikammertube, wobei eine erste Kammer die Zubereitung (A) und eine zweite Kammer die Zubereitung (B) aufnimmt. Es ist aber auch möglich, eine Mehrkammertube einzusetzen, die mehr als zwei Kammern, beispielsweise drei oder vier Kammern, aufweist. In diesem Fall kann Zubereitung (A) und/oder Zubereitung (B) auf mehrere Kammern der Mehrkammertube verteilt werden, wobei natürlich darauf zu achten ist, dass sich in einer bestimmten Kammer ausschließlich Zubereitung (A) oder Zubereitung (B) befindet.The two-component agent according to the invention is assembled in different chambers of a multi-chamber tube. The multi-chamber tube is preferably a two-chamber tube, a first chamber receiving the preparation (A) and a second chamber receiving the preparation (B). However, it is also possible to use a multi-chamber tube which has more than two chambers, for example three or four chambers. In this case, preparation (A) and / or preparation (B) can be distributed over several chambers of the multi-chamber tube, whereby it must of course be ensured that only preparation (A) or preparation (B) is in a particular chamber.
Zweikammertuben sind prinzipiell bereits im Stand der Technik bekannt. In einer besonders einfachen Ausführungsform haben die Tuben zwei getrennte Kammern, die als ineinandergesteckte Schläuche ausgebildet sind. Diese definieren die innere und die äußere Kammer und enden in dem gemeinsamen Kopf- oder Austrittsbereich. Der Kopfbereich ist derart gestaltet, dass die beiden Zubereitungen gemeinsam aus der Tube austreten, sobald Druck auf diese ausgeübt wird. Durch die Gestaltung des Kopfbereiches wird bestimmt, in welchem Streifenmuster die Zubereitungen aus der Tube austreten. Die bekannten handelsüblichen Tuben weisen ein gleiches Verhältnis der Volumina der Innentube zur Außentube und somit ein Mischungsverhältnis von 50 : 50 auf. Für Produkte, deren zwei Phasen getrennt aufbewahrt werden müssen und deren Mischungs- Verhältnis von dem herkömmlichen Wert von 50 : 50 abweicht, sind die bekannten Tuben nicht tauglich.In principle, two-chamber tubes are already known in the prior art. In a particularly simple embodiment, the tubes have two separate chambers, which are designed as nested tubes. These define the inner and the outer chamber and end in the common head or outlet area. The head area is designed in such a way that the two preparations exit the tube together as soon as pressure is exerted on it. The design of the head area determines the stripe pattern in which the preparations emerge from the tube. The known commercially available tubes have an equal ratio of the volumes of the inner tube to the outer tube and thus a mixing ratio of 50:50. For products whose two phases have to be kept separate and whose mixing If the ratio deviates from the conventional value of 50:50, the known tubes are not suitable.
Die erfindungsgemäßen Zweikomponentenmittel werden vorzugsweise in einer Zweikammertube konfektioniert, die eine innere und eine äußere Kammer aufweist, die beide in einem gemeinsamen Kopfbereich (Austrittsbereich) enden. Der Kopfbereich ist derart gestaltet, dass die beiden Zubereitungen gemeinsam aus der Tube austreten, sobald Druck auf diese ausgeübt wird. Durch die Gestaltung dieses Kopfbereiches wird bestimmt, in welchem Muster die Zubereitungen aus der Tube austreten.The two-component agents according to the invention are preferably assembled in a two-chamber tube which has an inner and an outer chamber, both of which end in a common head region (outlet region). The head area is designed in such a way that the two preparations exit the tube together as soon as pressure is exerted on it. The design of this head area determines the pattern in which the preparations emerge from the tube.
Die Wahl der Volumina der einzelnen Kammern richtet sich nach dem gewünschten Verhältnis der Volumina von Zubereitung (A) und Zubereitung (B) im Zweikomponentenmittel.The selection of the volumes of the individual chambers depends on the desired ratio of the volumes of preparation (A) and preparation (B) in the two-component agent.
Die bevorzugt eingesetzte Zweikammertube zeichnet sich insbesondere durch eine besondere Gestaltung des Austrittsbereiches aus. Hier spiegelt sich das Verhältnis der Kammervolumina in den Querschnitten der für die Teilströme definierten Wege wieder. Dabei sei darauf hingewiesen, dass der Teilstrom einer Zubereitung mehrere parallele Zweigströme aufweisen kann. So können Trennmittel den Querschnitt des Durchgangskanals zumindest nahezu entsprechend dem Verhältnis in zwei oder mehr Teilströme aufteilen. Dabei ist anzumerken, dass es für die Funktion der Zweikammertuben vorteilhaft ist, wenn die in den jeweiligen Tubenkammern vorhandenen verschiedenen Komponenten jeweils etwa die gleiche Viskosität aufweisen.The preferably used two-chamber tube is characterized in particular by a special design of the outlet area. The ratio of the chamber volumes is reflected here in the cross sections of the paths defined for the partial flows. It should be noted that the partial flow of a preparation can have several parallel branch flows. For example, separating agents can divide the cross-section of the through-channel into at least almost the ratio into two or more partial streams. It should be noted that it is advantageous for the function of the two-chamber tubes if the different components present in the respective tube chambers each have approximately the same viscosity.
Obwohl die Erfindung prinzipiell hinsichtlich des Musters, mit dem die Zubereitungen aus der Tube austreten, in keiner Weise beschränkt sein soll, kann es erfindungsgemäß bevorzugt sein, wenn die erste Zubereitung als Hauptstrang austritt und die zweite Zubereitung mehrere an diesem Hauptstrang entlanglaufende Streifen bildet. Auch hinsichtlich der Zahl dieser Streifen soll die Erfindung nicht eingeschränkt sein. Eine Zahl von 2 bis 4 Streifen kann erfindungsgemäß aus applikationstechnischen Gründen aber besonders bevorzugt sein. Dabei kann in einer ersten Ausgestaltungsform die Zubereitung (A) die Streifen bilden, während die Zubereitung (B) den Hauptstrang bildet und in einer zweiten Ausgestaltungsform die Zubereitung (B) die Streifen bilden, während die Zubereitung (A) den Hauptstrang bildet. In einer weiteren Ausgestaltungsform, kann es aber auch bevorzugt sein, wenn die beiden Zubereitungen anteilig gemeinsam nebeneinander den Hauptstrang bilden. In einer weiteren Ausgestaltungsform kann der Austrittsstrang aus einem inneren Bereich, gebildet aus einer ersten Zubereitung, und einem äußeren Bereich, gebildet aus der zweiten Zubereitung, bestehen, wobei die Zubereitungen entsprechend ihrer Anordnung in der Tube auch den Austrittsstrang bilden.Although the invention is in no way limited in principle with regard to the pattern with which the preparations emerge from the tube, it can be preferred according to the invention if the first preparation emerges as the main strand and the second preparation forms several strips running along this main strand. The invention should also not be restricted with regard to the number of these strips. According to the invention, however, a number of 2 to 4 strips can be particularly preferred for reasons of application technology. In a first embodiment, the preparation (A) forms the strips, while the preparation (B) forms the main strand, and in a second embodiment, the preparation (B) forms the strips, while the preparation (A) forms the main strand. In a further embodiment, however, it can also be preferred if the two preparations together form the main strand together. In a further embodiment, the outlet strand can consist of an inner region, formed from a first preparation, and an outer region, formed from the second preparation, the preparations also forming the outlet strand according to their arrangement in the tube.
Das Mengenverhältnis der Zubereitung (A) zur Menge der Zubereitung (B) liegt erfindungsgemäß bevorzugt in einem Bereich von 1 :2 bis 5:1 , ein Bereich von 1 :1 bis 3:1 ist erfindungsgemäß besonders bevorzugt.The ratio of the amount of preparation (A) to the amount of preparation (B) according to the invention is preferably in a range from 1: 2 to 5: 1, a range from 1: 1 to 3: 1 is particularly preferred according to the invention.
Prinzipiell soll die vorliegende Erfindung jede Verteilung der Kammern innerhalb der Tube umfassen. In einer ersten Ausführungsform können beispielsweise die beiden einzelnen Kammern nebeneinander in einer äußeren Hülle angeordnet sein. In einer erfindungsgemäß besonders bevorzugten Ausführungsform besteht die Zweikammertube aus einer inneren Tube, die von einer äußeren Tube vollständig umgeben ist. Diese Ausführungsform zeichnet sich durch eine optimal gleichbleibende Dosierung der beiden Zubereitungen aus. Obwohl prinzipiell jede Verteilung der Zubereitungen auf die Kammern der Tube erfindungsgemäß umfasst sein soll, kann es besonders bevorzugt sein, wenn die Zubereitung (A) sich in der Außentube befindet, und die Zubereitung (B) sich in der Innentube befindet.In principle, the present invention is intended to encompass any distribution of the chambers within the tube. In a first embodiment, for example, the two individual chambers can be arranged next to one another in an outer shell. In a particularly preferred embodiment according to the invention, the two-chamber tube consists of an inner tube which is completely surrounded by an outer tube. This embodiment is characterized by an optimally constant dosage of the two preparations. Although in principle every distribution of the preparations to the chambers of the tube is to be encompassed according to the invention, it can be particularly preferred if the preparation (A) is in the outer tube and the preparation (B) is in the inner tube.
Die Zweikammertube ist vorzugsweise aus einem Material gefertigt, dass zur Verpackung von Tönungs- und Färbemitteln dieser Art geeignet ist. Als erfindungsgemäß besonders geeignet hat sich sowohl für die Außenwände als auch für die Innenwände laminiertes Aluminium erwiesen. Es sind aber auch Tuben aus Kunststofflaminat (PE, PET, PP) oder Kunststoffcoextrudaten (PE, PET, PP) denkbar. Darüber hinaus kann in einer Ausführungsform das Material der Innentube unabhängig von dem Material der Außentube gewählt werden.The two-chamber tube is preferably made of a material that is suitable for packaging toning and coloring agents of this type. Laminated aluminum has proven particularly suitable according to the invention both for the outer walls and for the inner walls. However, tubes made of plastic laminate (PE, PET, PP) or plastic coextrudates (PE, PET, PP) are also conceivable. In addition, in one embodiment, the material of the inner tube can be selected independently of the material of the outer tube.
Als erfindungsgemäß ganz besonders bevorzugt hat sich eine Tube erwiesen, bei der die Innentube aus Aluminiumlaminat, das gegebenenfalls noch mit einem Lack geschützt ist, und die Außentube entweder aus Aluminiumlaminat oder aus Kunststofflaminat gefertigt ist. Unter Aluminiumlaminat wird erfindungsgemäß eine mit Kunststoff beschichtete Aluminiumschicht verstanden. Es ist besonders vorteilhaft, wenn der Schulterbereich der Außentube mit Ronden verstärkt wird, die besonders gute Barriereeigenschaften aufweisen. Dabei ist es vorteilhaft, in das Material der Ronden Aluminium einzuarbeiten.A tube in which the inner tube is made of aluminum laminate, which may also be protected with a lacquer, and the outer tube is made of either aluminum laminate or plastic laminate has proven to be particularly preferred according to the invention. According to the invention, aluminum laminate means an aluminum layer coated with plastic. It is particularly advantageous if the shoulder area of the outer tube is reinforced with round blanks which have particularly good barrier properties. It is advantageous to incorporate aluminum into the material of the round blanks.
Um ein Austreten der Mischung während der Lagerung zu verhindern und dem Verbraucher die Unversehrtheit der Tube zu versichern, ist es vorteilhaft, die Ausgabeöffnung mit einem Originalitätsverschluss aus Aluminium oder Kunststoff zu versiegeln, der vom Verbraucher entfernt wird.In order to prevent the mixture from escaping during storage and to ensure the integrity of the tube to the consumer, it is advantageous to seal the dispensing opening with a tamper-evident closure made of aluminum or plastic, which is removed by the consumer.
Die Zubereitungen (A) und (B) können neben den erfindungswesentlichen Komponenten weiterhin alle für solche Zubereitungen bekannten Wirk-, Zusatz- und Hilfsstoffe enthalten.In addition to the components essential to the invention, the preparations (A) and (B) can also contain all active ingredients, additives and auxiliaries known for such preparations.
In vielen Fällen enthalten die Färbemittel mindestens ein Tensid, wobei prinzipiell sowohl anionische als auch zwitterionische, ampholytische, nichtionische und kationische Tenside geeignet sind. In vielen Fällen hat es sich aber als vorteilhaft erwiesen, die Tenside aus anionischen, zwitterionischen oder nichtionischen Tensiden auszuwählen.In many cases, the colorants contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.
Als anionische Tenside eignen sich in erfindungsgemäßen Zubereitungen alle für die Verwendung am menschlichen Körper geeigneten anionischen oberflächenaktiven Stoffe. Diese sind gekennzeichnet durch eine wasserlöslichmachende, anionische Gruppe wie z. B. eine Carboxylat-, Sulfat-, Sulfonat- oder Phosphat-Gruppe und eine lipophile Alkyl- gruppe mit etwa 10 bis 22 C-Atomen. Zusätzlich können im Molekül Glykol- oder Poly- glykolether-Gruppen, Ester-, Ether- und Amidgruppen sowie Hydroxylgruppen enthalten sein. Beispiele für geeignete anionische Tenside sind, jeweils in Form der Natrium-, Kalium- und Ammonium- sowie der Mono-, Di- und Trialkanolammoniumsalze mit 2 oder 3 C-Atomen in der Alkanolgruppe, lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen), Ethercarbonsäuren der Formel R-0-(CH2-CH20)x -CH2-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist, Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe, Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe, Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe, Sulfobemsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobemsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C- Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen, lineare Alkansulfonate mit 12 bis 18 C-Atomen, lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen, Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen, Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-0(CH2-CH20)x-S03H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist, Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030, sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354, Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344, Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps ), Ether carboxylic acids of the formula R-0- (CH 2 -CH 2 0) x -CH 2 -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 up to 18 C atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid mono alkyl polyoxyethyl esters with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 C atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula R-0 (CH 2 -CH 2 0) x -S0 3 H, in which R a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12, mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354, sulfonates unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344, esters of tartaric acid and citric acid with alcohols, the adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 Represent carbon atoms.
Bevorzugte anionische Tenside sind Alkylsulfate, Alkylpolyglykolethersulfate und Ether- carbonsäuren mit 10 bis 18 C-Atomen in der Alkylgruppe und bis zu 12 Glykolethergrup- pen im Molekül sowie insbesondere Salze von gesättigten und insbesondere ungesättigten C8-C22-Carbonsäuren, wie Ölsäure, Stearinsäure, Isostearinsäure und Palmitinsäure.Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C 8 -C 22 carboxylic acids, such as oleic acid, stearic acid , Isostearic acid and palmitic acid.
Nichtionogene Tenside enthalten als hydrophile Gruppe z. B. eine Poiyolgruppe, eine Po- lyalkylenglykolethergruppe oder eine Kombination aus Polyol- und Polyglykolethergruppe. Solche Verbindungen sind beispielsweise Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 1 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C- Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe, C12-C22-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin, C8-C22-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowie Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.Non-ionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such compounds are, for example, adducts of 2 to 30 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group, C 12 -C 22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol, C 8 -C 22 alkyl mono- and oligoglycosides and their ethoxylated analogues, and adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.
Bevorzugte nichtionische Tenside sind Alkylpolyglykoside der allgemeinen Formel R10- (Z)χ. Diese Verbindungen sind durch die folgenden Parameter gekennzeichnet. Der Alkylrest R1 enthält 6 bis 22 Kohlenstoffatome und kann sowohl linear als auch verzweigt sein. Bevorzugt sind primäre lineare und in 2-Stellung methylverzweigte aliphati- sche Reste. Solche Alkylreste sind beispielsweise 1-Octyl, 1-Decyl, 1-Lauryl, 1-Myristyl, 1- Cetyl und 1-Stearyl. Besonders bevorzugt sind 1 -Octyl, 1-Decyl, 1-Lauryl, 1-Myristyl. Bei Verwendung sogenannter "Oxo-Alkohole" als Ausgangsstoffe überwiegen Verbindungen mit einer ungeraden Anzahl von Kohlenstoffatomen in der Alkylkette.Preferred nonionic surfactants are alkyl polyglycosides of the general formula R 1 0- (Z) χ . These connections are characterized by the following parameters. The alkyl radical R 1 contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.
Die erfindungsgemäß verwendbaren Alkylpolyglykoside können beispielsweise nur einen bestimmten Alkylrest R1 enthalten. Üblicherweise werden diese Verbindungen aber ausgehend von natürlichen Fetten und Ölen oder Mineralölen hergestellt. In diesem Fall liegen als Alkylreste R Mischungen entsprechend den Ausgangsverbindungen bzw. entsprechend der jeweiligen Aufarbeitung dieser Verbindungen vor.The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R 1 . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.
Besonders bevorzugt sind solche Alkylpolyglykoside, bei denen R1 im wesentlichen aus C8- und C10-Alkylgruppen, im wesentlichen aus C12- und C1 -Alkylgruppen, im wesentlichen aus C8- bis C16-Alkylgruppen oder im wesentlichen aus C12- bis C16-Alkylgruppen besteht.Particularly preferred are those alkyl polyglycosides in which R 1 essentially consists of C 8 and C 10 alkyl groups, essentially from C 12 and C 1 alkyl groups, essentially from C 8 to C 16 alkyl groups or essentially from C 12 - to C 16 alkyl groups.
Als Zuckerbaustein Z können beliebige Mono- oder Oligosaccharide eingesetzt werden. Üblicherweise werden Zucker mit 5 bzw. 6 Kohlenstoffatomen sowie die entsprechenden Oligosaccharide eingesetzt. Solche Zucker sind beispielsweise Glucose, Fructose, Galactose, Arabinose, Ribose, Xylose, Lyxose, Allose, Altrose, Mannose, Gulose, Idose, Talose und Sucrose. Bevorzugte Zuckerbausteine sind Glucose, Fructose, Galactose, Arabinose und Sucrose; Glucose ist besonders bevorzugt.Any mono- or oligosaccharides can be used as the sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.
Die erfindungsgemäß verwendbaren Alkylpolyglykoside enthalten im Schnitt 1 ,1 bis 5 Zuckereinheiten. Alkylpolyglykoside mit x-Werten von 1,1 bis 1 ,6 sind bevorzugt. Ganz besonders bevorzugt sind Alkylglykoside, bei denen x 1 ,1 bis 1,4 beträgt.The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.
Die Alkylglykoside können neben ihrer Tensidwirkung auch dazu dienen, die Fixierung von Duftkomponenten auf dem Haar zu verbessern. Der Fachmann wird also für den Fall, dass eine über die Dauer der Haarbehandlung hinausgehende Wirkung des Parfümöles auf dem Haar gewünscht wird, bevorzugt zu dieser Substanzklasse als weiterem Inhaltsstoff der erfindungsgemäßen Zubereitungen zurückgreifen. Auch die alkoxylierten Homologen der genannten Alkylpolyglykoside können erfindungsgemäß eingesetzt werden. Diese Homologen können durchschnittlich bis zu 10 Ethylenoxid- und/oder Propylenoxideinheiten pro Alkylglykosideinheit enthalten.In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. In the event that an effect of the perfume oil on the hair beyond the duration of the hair treatment is desired, the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention. The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.
Weiterhin können, insbesondere als Co-Tenside, zwitterionische Tenside verwendet werden. Als zwitterionische Tenside werden solche oberflächenaktive Verbindungen bezeichnet, die im Molekül mindestens eine quartäre Ammoniumgruppe und mindestens eine -COOH- oder -S03 (_)-Gruppe tragen. Besonders geeignete zwitterionische Tenside sind die sogenannten Betaine wie die N-Alkyl-N,N-dimethylammonium-glycinate, beispielsweise das Kokosalkyl-dimethylammonium-glycinat, N-Acyl-aminopropyl-N,N-di- methylammoniumglycinate, beispielsweise das Kokosacylaminopropyl-dimethyl- ammoniumglycinat, und 2-Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazoline mit jeweils 8 bis 18 C-Atomen in der Alkyl- oder Acylgruppe sowie das Kokosacylaminoethylhydroxy- ethylcarboxymethylglycinat. Ein bevorzugtes zwitterionisches Tensid ist das unter der INCI-Bezeichnung Cocamidopropyl Betaine bekannte Fettsäureamid-Derivat.Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO H - or -S0 3 (_) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethyl- ammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.
Ebenfalls insbesondere als Co-Tenside geeignet sind ampholytische Tenside. Unter am- pholytischen Tensiden werden solche oberflächenaktiven Verbindungen verstanden, die außer einer C8-C18-Alkyl- oder Acylgruppe im Molekül mindestens eine freie Aminogruppe und mindestens eine -COOH- oder -S03H-Gruppe enthalten und zur Ausbildung innerer Salze befähigt sind. Beispiele für geeignete ampholytische Tenside sind N-Alkylglycine, N-Alkylpropionsäuren, N-Alkylaminobuttersäuren, N-Alkyliminodipropionsäuren, N- Hydroxyethyl-N-alkylamidopropylglycine, N-Alkyltaurine, N-Alkylsarcosine, 2-Alkylamino- propionsäuren und Alkylaminoessigsäuren mit jeweils etwa 8 bis 18 C-Atomen in der Alkylgruppe. Besonders bevorzugte ampholytische Tenside sind das N-Kokosalkyl- aminopropionat, das Kokosacylaminoethylaminopropionat und das C12-18-Acylsarcosin.Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C 8 -C 18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -S0 3 H group in the molecule and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylamino propionic acid and alkylamino acetic acid each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and C 12-18 acyl sarcosine.
Erfindungsgemäß werden als kationische Tenside insbesondere solche vom Typ der quartären Ammoniumverbindungen, der Esterquats und der Amidoamine eingesetzt.According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound, esterquat and amidoamine type.
Bevorzugte quartäre Ammoniumverbindungen sind Ammoniumhalogenide, insbesondere Chloride und Bromide, wie Alkyltrimethylammoniumchloride, Dialkyldimethylammonium- chloride und Trialkylmethylammoniumchloride, z. B. Cetyltrimethylammoniumchlorid, Stearyltrimethylammoniumchlorid, Distearyldimethylammoniumchlorid, Lauryldimethyl- ammoniumchlorid, Lauryldimethylbenzylammoniumchlorid und Tricetylmethylammonium- chlorid, sowie die unter den INCI-Bezeichnungen Quaternium-27 und Quaternium-83 bekannten Imidazolium-Verbindungen. Die langen Alkylketten der oben genannten Tenside weisen bevorzugt 10 bis 18 Kohlenstoffatome auf.Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.
Bei Esterquats handelt es sich um bekannte Stoffe, die sowohl mindestens eine Esterfunktion als auch mindestens eine quartäre Ammoniumgruppe als Strukturelement enthalten. Bevorzugte Esterquats sind quaternierte Estersalze von Fettsäuren mit Trietha- nolamin, quaternierte Estersalze von Fettsäuren mit Diethanolalkylaminen und quater- nierten Estersalze von Fettsäuren mit 1 ,2-Dihydroxypropyldialkylaminen. Solche Produkte werden beispielsweise unter den Warenzeichen Stepantex®, Dehyquart® und Armocare® vertrieben. Die Produkte Armocare® VGH-70, ein N,N-Bis(2-Palmitoyloxyethyl)dimethyl- ammoniumchlorid, sowie Dehyquart® F-75 und Dehyquart® AU-35 sind Beispiele für solche Esterquats.Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines. Such products are sold, for example, under the trademarks Stepantex ® , Dehyquart ® and Armocare ® . The products Armocare ® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, and Dehyquart ® F-75 and Dehyquart ® AU-35 are examples of such esterquats.
Die Alkylamidoamine werden üblicherweise durch Amidierung natürlicher oder synthetischer Fettsäuren und Fettsäureschnitte mit Dialkylaminoaminen hergestellt. Eine erfindungsgemäß besonders geeignete Verbindung aus dieser Substanzgruppe stellt das unter der Bezeichnung Tegoamid® S 18 im Handel erhältliche Stearamidopropyl- dimethylamin dar.The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances that available under the name Tegoamid ® S 18 commercially stearamidopropyldimethylamine is dimethylamine.
Weitere erfindungsgemäß verwendbare kationische Tenside stellen die quaternisierten Proteinhydrolysate dar.The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.
Erfindungsgemäß ebenfalls geeignet sind kationische Silikonöle wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trime- thylsilylamodimethicon), Dow Corning 929 Emulsion (enthaltend ein hydroxylamino-mo- difiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydimethylsiloxane, Quaternium-80).Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).
Ein Beispiel für ein als kationisches Tensid einsetzbares quaternäres Zuckerderivat stellt das Handelsprodukt Glucquat®100 dar, gemäß INCI-Nomenklatur ein "Lauryl Methyl Glu- ceth-10 Hydroxypropyl Dimonium Chloride".An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".
Bei den als Tensid eingesetzten Verbindungen mit Alkylgruppen kann es sich jeweils um einheitliche Substanzen handeln. Es ist jedoch in der Regel bevorzugt, bei der Herstellung dieser Stoffe von nativen pflanzlichen oder tierischen Rohstoffen auszugehen, so dass man Substanzgemische mit unterschiedlichen, vom jeweiligen Rohstoff abhängigen Alkyl- kettenlängen erhält.The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is usually preferred in manufacturing These substances are based on natural vegetable or animal raw materials, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.
Bei den Tensiden, die Anlagerungsprodukte von Ethylen- und/oder Propylenoxid an Fettalkohole oder Derivate dieser Anlagerungsprodukte darstellen, können sowohl Produkte mit einer "normalen" Homologenverteilung als auch solche mit einer eingeengten Homologenverteilung verwendet werden. Unter "normaler" Homologenverteilung werden dabei Mischungen von Homologen verstanden, die man bei der Umsetzung von Fettalkohol und Alkylenoxid unter Verwendung von Alkalimetallen, Alkalimetallhydroxiden oder Alkalime- tallalkoholaten als Katalysatoren erhält. Eingeengte Homologenverteilungen werden dagegen erhalten, wenn beispielsweise Hydrotaicite, Erdalkalimetallsalze von Ethercarbonsäuren, Erdalkalimetalloxide, -hydroxide oder -alkoholate als Katalysatoren verwendet werden. Die Verwendung von Produkten mit eingeengter Homologenverteilung kann bevorzugt sein.In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. On the other hand, narrow homolog distributions are obtained if, for example, hydrotaicites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.
Ferner können die erfindungsgemäßen Färbemittel weitere Wirk-, Hilfs- und Zusatzstoffe, wie beispielsweise nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane, kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl- ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino- ethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazolinium- methochlorid-Copolymere und quaternierter Polyvinylalkohol, zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-tri- methylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacry- lat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere, anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobomylacrylat-Copolymere, Methylvinylether/Malein- säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid- Terpolymere,Furthermore, the colorants according to the invention can contain further active ingredients, auxiliaries and additives, such as, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysilammonones, with quaternary chloride groups, with quaternary chloride groups , Acrylamide-dimethyldiallyl-ammonium chloride copolymers, with diethyl sulfate quaternized dimethylamino-ethyl methacrylate-vinyl pyrrolidone copolymers, vinyl pyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers / such as acrylamidyl amide / methyl acrylamido propyl chloride / acrylamido-amyl propyl / acrylamethyl-aminopropyl chloride -methacry- lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, cross-linked polyacrylic acids, vinyl acetate / crotonic acid copolymers , Vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobomylacrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,
- Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi ara- bicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcel- lulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z.B. Polyvinylalkohol, Strukturanten wie Maleinsäure und Milchsäure, haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,- Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, for. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethylcel lulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,
Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quatemisierte Proteinhydrolysate, Parfümöle, Dimethylisosorbid und Cyclodextrine,Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,
Lösungsmittel und -Vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol, faserstrukturverbessemde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose, quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat Entschäumer wie Silikone, Farbstoffe zum Anfärben des Mittels,Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, active substances that improve fiber structure, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2 alkylimidazolinium methosulfate defoamers such as silicones, dyes for coloring the agent,
Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol, Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,Substances for adjusting the pH, such as customary acids, in particular edible acids and bases,
Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol, Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B3, B5, Bβ, C, E, F und H,Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts as well as bisabolol, vitamins, provitamins and vitamin precursors, in particular those of groups A, B 3 , B 5 , B β , C, E, F and H,
Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennnessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Rosskastanie, Sandelholz, Wacholder, Kokosnuss, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,. Cholesterin,Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root. Cholesterol,
Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether, Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine, Fettsäurealkanolamide, Komplexbildner wie EDTA, NTA, ß-Alanindiessigsäure und Phosphonsäuren, - Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,Consistency agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides, complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids, Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
- Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat, Konservierungsmittel, Stabilisierungsmittel für Wasserstoffperoxid und andere Oxidationsmittel,Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, preservatives, stabilizers for hydrogen peroxide and other oxidizing agents,
- Treibmittel wie Propan-Butan-Gemische, N20, Dimethylether, C02 und Luft,- blowing agents such as propane-butane mixtures, N 2 0, dimethyl ether, C0 2 and air,
- Antioxidantien, enthalten.- contain antioxidants.
Bezüglich weiterer fakultativer Komponenten sowie die eingesetzten Mengen dieser Komponenten wird ausdrücklich auf die dem Fachmann bekannten einschlägigen Handbücher, z. B. Kh. Schrader, Grundlagen und Rezepturen der Kosmetika, 2. Auflage, Hüthig Buch Verlag, Heidelberg, 1989, verwiesen.With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, e.g. B. Kh. Schrader, Fundamentals and Recipes of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.
Die Zubereitungen (A) und (B) enthalten die erfindungswesentlichen Komponenten erfindungsgemäß bevorzugt in einem geeigneten wässrigen, alkoholischen oder wässrig- alkoholischen Träger. Zum Zwecke der Haarfärbung sind solche Träger beispielsweise Cremes, Emulsionen, Gele oder auch tensidhaltige schäumende Lösungen, wie beispielsweise Shampoos, Schaumaerosole oder andere Zubereitungen, die für die Anwendung auf dem Haar geeignet sind.Preparations (A) and (B) preferably contain the components essential to the invention in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair.
Unter wässrig-alkoholischen Lösungen sind im Sinne der vorliegenden Erfindung wässrige Lösungen enthaltend 3 bis 70 Gew.-% eines d-C4-Alkohols, insbesondere Ethanol bzw. Isopropanol, zu verstehen. Die erfindungsgemäßen Mittel können zusätzlich weitere organische Lösemittel, wie beispielsweise Methoxybutanol, Benzylalkohol, Ethyldiglykol oder 1,2-Propylenglykol, enthalten. Bevorzugt sind dabei alle wasserlöslichen organischen Lösemittel.For the purposes of the present invention, aqueous-alcoholic solutions are understood to mean aqueous solutions containing 3 to 70% by weight of a dC 4 alcohol, in particular ethanol or isopropanol. The agents according to the invention can additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred.
Weiterhin können die erfindungsgemäßen Zweikomponentenmittel ein Reduktionsmittel enthalten. Beispiele für erfindungsgemäß bevorzugte Reduktionsmittel sind Natriumsulfit, Ascorbinsäure, Thioglykolsäure und deren Derivate, Natriumthionit, Alkalimetallcitratsalze und N-Acetyl-L-Cystein Ganz besonders bevorzugte Reduktionsmittel sind Alkalimetallcitratsalze, insbesondere Natriumeitrat, und N-Acetyl-L-Cystein. N-Acetyl-L-Cystein ist ein ganz besonders bevorzugtes Reduktionsmittel. Weiterhin können die erfindungsgemäßen Mittel Alkalisierungsmittel, üblicherweise Alkalioder Erdalkalihydroxide, Ammoniak oder organische Amine, enthalten. Bevorzugte Alkalisierungsmittel sind Monoethanolamin, Monoisopropanolamin, 2-Amino-2-methyl- propanol, 2-Amino-2-methyl-1 ,3-propandiol, 2-Amino-2-ethyl-1 ,3-propandiol, 2-Amino-2- methylbutanol und Triethanolamin sowie Alkali- und Erdalkalimetallhydroxide. Insbesondere Monoethanolamin, Triethanolamin sowie 2-Amino-2-methyl-propanol und 2- Amino-2-methyl-1 ,3-propandiol sind im Rahmen dieser Gruppe bevorzugt. Auch die Verwendung von ω-Aminosäuren wie ω-Aminocapronsäure als Alkalisierungsmittel ist möglich.Furthermore, the two-component agents according to the invention can contain a reducing agent. Examples of preferred reducing agents according to the invention are sodium sulfite, ascorbic acid, thioglycolic acid and their derivatives, sodium thionite, alkali metal citrate salts and N-acetyl-L-cysteine. Particularly preferred reducing agents are alkali metal citrate salts, in particular sodium citrate, and N-acetyl-L-cysteine. N-acetyl-L-cysteine is a very particularly preferred reducing agent. The agents according to the invention can furthermore contain alkalizing agents, usually alkali or alkaline earth metal hydroxides, ammonia or organic amines. Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1, 3-propanediol, 2-amino-2 - methylbutanol and triethanolamine as well as alkali and alkaline earth metal hydroxides. Monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanediol are particularly preferred in this group. The use of ω-amino acids such as ω-aminocaproic acid as an alkalizing agent is also possible.
Häufig werden zu diesem Zweck Perlglanzpigmente eingesetzt. Erfindungsgemäß bevorzugte Perlglanzpigmente sind natürliche Perlglanzpigmente wie z.B. Fischsilber (Guanin/Hypoxanthin-Mischkristalle aus Fischschuppen) oder Perlmutt (aus vermahlenen Muschelschalen), monokristalline Perlglanzpigmente wie z.B. Bismutoxychlorid, sowie Perlglanzpigmente auf Basis von Glimmer oder Glimmer/Metalloxid. Letztgenannte Perlglanzpigmente werden mit einem Metalloxidcoating versehen. Durch den Einsatz der Perlglanzpigmente werden Glanz und gegebenenfalls zusätzlich Farbeffekte in den erfindungsgemäßen Zweikomponentenmitteln erzielt. Die Farbgebung durch die in den Zweikomponentenmitteln verwendeten Perlglanzpigmente beeinflusst das Farbergebnis der Färbung der Keratinfasern jedoch nicht.Pearlescent pigments are often used for this purpose. Pearlescent pigments preferred according to the invention are natural pearlescent pigments such as e.g. Fish silver (guanine / hypoxanthine mixed crystals from fish scales) or mother-of-pearl (from ground mussel shells), monocrystalline pearlescent pigments such as Bismuth oxychloride and pearlescent pigments based on mica or mica / metal oxide. The latter pearlescent pigments are provided with a metal oxide coating. By using the pearlescent pigments, sheen and optionally additional color effects are achieved in the two-component agents according to the invention. However, the coloring due to the pearlescent pigments used in the two-component agents does not influence the color result of the coloring of the keratin fibers.
Perlglanzpigmente auf Glimmer-Basis und auf Glimmer/Metalloxid-Basis sind erfindungsgemäß ebenfalls bevorzugt. Glimmer gehören zu den Schicht-Silicaten. Die wichtigsten Vertreter dieser Silicate sind Muscovit, Phlogopit, Paragonit, Biotit, Lepidolith und Margarit. Zur Herstellung der Perlglanzpigmente in Verbindung mit Metalloxiden wird der Glimmer, überwiegend Muscovit oder Phlogopit, mit einem Metalloxid beschichtet. Geeignete Metalloxide sind u.a. Ti02, Cr203 und Fe203. Durch entsprechende Beschichtung werden Interferenzpigmente sowie Farbglanzpigmente als erfindungsgemäße Perlglanzpigmente erhalten. Diese Perlglanzpigmentarten weisen neben einem glitzernden optischen Effekt zusätzlich Farbeffekte auf. Des weiteren können die erfindungsgemäß verwendbaren Perlglanzpigmente weiterhin ein Farbpigment enthalten, welches sich nicht von einem Metalloxid ableitet. Die Korngröße der bevorzugt verwendeten Perlglanzpigmente liegt bevorzugt zwischen 1.0 und 100 μm, besonders bevorzugt zwischen 5.0 und 60.0 μm.Pearlescent pigments based on mica and on mica / metal oxide are also preferred according to the invention. Mica is one of the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce the pearlescent pigments in conjunction with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide. Suitable metal oxides include Ti0 2 , Cr 2 0 3 and Fe 2 0 3 . Corresponding coatings and interference luster pigments are obtained as pearlescent pigments according to the invention by means of a corresponding coating. In addition to a glittering optical effect, these types of pearlescent pigment also have color effects. Furthermore, the pearlescent pigments which can be used according to the invention can furthermore contain a color pigment which is not derived from a metal oxide. The grain size of the preferably used pearlescent pigments is preferably between 1.0 and 100 μm, particularly preferably between 5.0 and 60.0 μm.
Besonders bevorzugte Periglanzpigmente sind Pigmente, die von der Firma Merck unter den Handelsnamen Colorona® vermarktet werden, wobei die Pigmente Colorona® red- brown (47-57 Gew.% Muscovit Mica (KH2(AISi04)3), 43-50 Gew.% Fe203 (INCI: Iran Oxides Cl 77491), <3 Gew.% Ti02 (INCI: Titanium Dioxide Cl 77891), Colorona® Blackstar Blue (39-47 Gew.% Muscovit Mica (KH2(AISi04)3), 53-61 Gew.% Fe304 (INCI: Iran Oxides Cl 77499)), Colorona® Siena Fine (35-45 Gew.% Muscovit Mica (KH2(AISi04)3), 55-65 Gew.% Fe203 (INCI: Iran Oxides Cl 77491)), Colorona® Aborigine Amber (50-62 Gew.% Muscovit Mica (KH2(AISi04)3), 36-44 Gew.% Fe304 (INCI: Iran Oxides Cl 77499), 2-6 Gew.% Ti02 (INCI: Titanium Dioxide Cl 77891)), Colorona® Patagonian Purple (42-54 Gew.% Muscovit Mica (KH2(AISi04)3), 26-32 Gew.% Fe203 (INCI: Iran Oxides Cl 77491), 18-22 Gew.% Ti02 (INCI: Titanium Dioxide Cl 77891), 2-4 Gew.% Preussisch Blau (INCI: Ferric Ferrocyanide Cl 77510)), Colorona® Chameleon (40-50 Gew.% Muscovit Mica (KH2(AISi04)3), 50-60 Gew.% Fe203 (INCI: Iran Oxides Cl 77491)) und Silk® Mica ( >98 Gew.% Muscovit Mica (KH2(AISi04)3)) ganz besonders bevorzugt sind.Particularly preferred pearlescent pigments are pigments which are marketed by the Merck company under the trade name Colorona ® , the pigments Colorona ® red-brown (47-57% by weight Muscovit Mica (KH 2 (AISi0 4 ) 3 ), 43-50% by weight % Fe 2 0 3 (INCI: Iran Oxides Cl 77491), <3% by weight Ti0 2 (INCI: Titanium Dioxide Cl 77891), Colorona ® Blackstar Blue (39-47% by weight Muscovit Mica (KH 2 (AISi0 4 .) 3), 53-61% by weight of Fe 3 0 4 (INCI: Iran oxide Cl 77499)), Colorona ® Fine Siena (35-45% by weight of muscovite mica (KH 2 (AISi0 4) 3), 55-65. % Fe 2 0 3 (INCI: Iran Oxides Cl 77491)), Colorona ® Aboriginal Amber (50-62% by weight Muscovit Mica (KH 2 (AISi0 4 ) 3 ), 36-44% by weight Fe 3 0 4 (INCI: Iran Oxides Cl 77499), 2-6% by weight Ti0 2 (INCI: Titanium Dioxide Cl 77891)), Colorona ® Patagonian Purple (42-54% by weight Muscovit Mica (KH 2 (AISi0 4 ) 3 ), 26-32% by weight Fe 2 0 3 (INCI: Iran Oxides Cl 77491), 18-22% by weight Ti0 2 (INCI: Titanium Dioxide Cl 77891), 2-4% by weight Prussian Blue (INCI: Ferric Ferrocyanide Cl 77510 )), Colorona ® Chameleon (40-50% by weight Muscovit Mica (KH 2 (AISi0 4 ) 3 ), 50-60% by weight Fe 2 0 3 (INCI: Iran Oxides Cl 77491)) and Silk ® Mica (> 98 wt.% Muscovit Mica (KH 2 (AISi0 4 ) 3 )) are very particularly preferred.
Bezüglich der in den erfindungsgemäßen Zweikomponentenmitteln einsetzbaren Periglanzpigmente wird weiterhin ausdrücklich auf die Monographien Inorganic Pigments, Chemical technology review Nr. 166, 1980, Seiten 161-173 (ISBN 0-8155-0811-5) und Industrial inorganic Pigments, 2. Auflage, Weinheim, VCH, 1998, Seiten 211-231 , Bezug genommen.With regard to the pearlescent pigments which can be used in the two-component compositions according to the invention, reference is also expressly made to the monographs Inorganic Pigments, Chemical technology review No. 166, 1980, pages 161-173 (ISBN 0-8155-0811-5) and Industrial inorganic Pigments, 2nd edition, Weinheim , VCH, 1998, pages 211-231.
Die eigentliche oxidative Färbung der Fasern kann grundsätzlich mit Luftsauerstoff erfolgen. Bevorzugt wird jedoch ein chemisches Oxidationsmittel eingesetzt, besonders dann, wenn neben der Färbung ein Aufhelleffekt an menschlichem Haar gewünscht ist. Als Oxidationsmittel kommen Persulfate, Chlorite und insbesondere Wasserstoffperoxid oder dessen Anlagerungsprodukte an Harnstoff, Melamin sowie Natriumborat in Frage. Erfindungsgemäß kann aber das Oxidationsfärbemittel auch zusammen mit einem Katalysator auf das Haar aufgebracht werden, der die Oxidation der Farbstoffvorprodukte, z.B. durch Luftsauerstoff, aktiviert. Solche Katalysatoren sind z.B. Metallionen, lodide, Chinone oder bestimmte Enzyme. Geeignete Metallionen sind beispielsweise Zn2+, Cu2+, Fe2+, Fe3+, Mn20 Mn4+, Li+, Mg2+, Ca2+ und Al3+. Besonders geeignet sind dabei Zn2\ Cu2+ und Mn2+. Die Metallionen können prinzipiell in der Form eines beliebigen, physiologisch verträglichen Salzes oder in Form einer Komplexverbindung eingesetzt werden. Bevorzugte Salze sind die Acetate, Sulfate, Halogenide, Lactate und Tartrate. Durch Verwendung dieser Metallsalze kann sowohl die Ausbildung der Färbung beschleunigt als auch die Farbnuance gezielt beeinflusst werden.The actual oxidative coloring of the fibers can basically be done with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. According to the invention, however, the oxidation coloring agent can also be applied to the hair together with a catalyst which activates the oxidation of the dye precursors, for example by atmospheric oxygen. Such catalysts are, for example, metal ions, iodides, quinones or certain enzymes. Suitable metal ions are, for example, Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2 0 Mn 4+ , Li + , Mg 2+ , Ca 2+ and Al 3+ . Zn 2 \ Cu 2+ and Mn 2+ are particularly suitable. In principle, the metal ions can be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner.
Geeignete Enzyme sind z.B. Peroxidasen, die die Wirkung geringer Mengen an Wasserstoffperoxid deutlich verstärken können. Weiterhin sind solche Enzyme erfindungsgemäß geeignet, die mit Hilfe von Luftsauerstoff die Oxidationsfarbstoffvorprodukte direkt oxidieren, wie beispielsweise die Laccasen, oder in situ geringe Mengen Wasserstoffperoxid erzeugen und auf diese Weise die Oxidation der Farbstoffvorprodukte bio- katalytisch aktivieren. Besonders geeignete Katalysatoren für die Oxidation der Farbstoffvorläufer sind die sogenannten 2-Elektronen-Oxidoreduktasen in Kombination mit den dafür spezifischen Substraten, z.B. Pyranose-Oxidase und z.B. D-Glucose oder Galactose, Glucose-Oxidase und D-Glucose, Glycerin-Oxidase und Glycerin, Pyruvat-Oxidase und Brenztraubensäure oder deren Salze, - Alkohol-Oxidase und Alkohol (MeOH, EtOH), Lactat-Oxidase und Milchsäure und deren Salze, Tyrosinase-Oxidase und Tyrosin, Uricase und Harnsäure oder deren Salze, Cholinoxidase und Cholin, Aminosäure-Oxidase und Aminosäuren.Suitable enzymes are e.g. Peroxidases, which can significantly increase the effects of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and thus bio-catalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific for this, e.g. Pyranose oxidase and e.g. D-glucose or galactose, glucose oxidase and D-glucose, glycerin oxidase and glycerin, pyruvate oxidase and pyruvic acid or their salts, - alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and their salts, Tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and amino acids.
Das eigentliche Haarfärbemittel wird zweckmäßigerweise unmittelbar vor der Anwendung durch Mischung der Zubereitung eines Oxidationsmittels mit den aus der Tube ausgebrachten Zubereitungen (A) und (B) hergestellt. Das dabei entstehende gebrauchsfertige Haarfärbepräparat sollte bevorzugt einen pH-Wert im Bereich von 6 bis 12 aufweisen. Sofern nichts anderes vermerkt ist, ist unter den Angaben zum pH-Wert im Rahmen der vorliegenden Offenbarung der pH-Wert bei 25°C zu verstehen. Besonders bevorzugt ist die Anwendung der Haarfärbemittel in einem alkalischen Milieu. Die Anwendungstemperaturen können in einem Bereich zwischen 15 und 40 °C liegen. Nach einer Einwirkungszeit von 5 bis 45 Minuten wird das Haarfärbemittel durch Ausspülen von dem zu färbenden Haar entfernt. Das Nachwaschen mit einem Shampoo entfällt, wenn ein stark tensid haltiger Träger, z.B. ein Färbeshampoo, verwendet wurde.The actual hair dye is expediently prepared immediately before use by mixing the preparation of an oxidizing agent with the preparations (A) and (B) applied from the tube. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. Unless otherwise stated, the information on the pH value within the scope of the present disclosure is to be understood as the pH value at 25 ° C. The use of hair dyes in an alkaline environment is particularly preferred. Application temperatures can range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes, the hair dye is rinsed out of it staining hair removed. Washing with a shampoo is not necessary if a carrier with a high tenside content, such as a coloring shampoo, has been used.
Insbesondere bei schwer färbbarem Haar kann das Zweikomponentenmittel aber auch ohne vorherige Vermischung mit der Oxidationskomponente auf das Haar aufgebracht und einmassiert werden. Nach einer Einwirkdauer von 20 bis 30 Minuten wird dann - gegebenenfalls nach einer Zwischenspülung - die Oxidationskomponente aufgebracht. Nach einer weiteren Einwirkdauer von 10 bis 20 Minuten wird dann gespült und gewünschtenfalls nachshampooniert. Bei dieser Ausführungsform wird gemäß einer ersten Variante, bei der das vorherige Aufbringen der Farbstoffvorprodukte eine bessere Penetration in das Haar bewirken soll, das entsprechende Mittel auf einen pH-Wert von etwa 4 bis 7 eingestellt. Gemäß einer zweiten Variante wird zunächst eine Luftoxidation angestrebt, wobei das aufgebrachte Mittel bevorzugt einen pH-Wert von 7 bis 10 aufweist. Bei der anschließenden beschleunigten Nachoxidation kann die Verwendung von sauer eingestellten Peroxidisulfat-Lösungen als Oxidationsmittel bevorzugt sein.Particularly in the case of hair that is difficult to dye, the two-component agent can also be applied to the hair and massaged in without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if necessary after an intermediate rinse. After a further exposure time of 10 to 20 minutes, rinsing is then carried out and, if desired, re-shampooing. In this embodiment, according to a first variant, in which the previous application of the dye precursors is supposed to bring about better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, air oxidation is initially aimed for, the agent applied preferably having a pH of 7 to 10. In the subsequent accelerated postoxidation, the use of acidified peroxidisulfate solutions as the oxidizing agent can be preferred.
Die Zubereitungen (A) und (B) des erfindungsgemäßen Zweikomponentenmittels weisen vorzugsweise Viskositäten im Bereich von 2 000 bis 200 000 mPas, insbesondere von 5 000 bis 50 000 mPas (Brookfield-Viskosimeter, Spindel Nr. 4, 20 rpm, 20°C) auf. Auf diese Weise ist gewährleistet, dass das Zweikomponentenmittel eine gute Mischbarkeit aufweist und dennoch das Austrittsmuster eine hinreichende Stabilität aufweist.Preparations (A) and (B) of the two-component agent according to the invention preferably have viscosities in the range from 2,000 to 200,000 mPas, in particular from 5,000 to 50,000 mPas (Brookfield viscometer, spindle no. 4, 20 rpm, 20 ° C.) on. This ensures that the two-component agent has good miscibility and nevertheless the exit pattern has sufficient stability.
Ein zweiter Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Färbung von keratinischen Fasern, insbesondere menschlichen Haaren, wobei ein erfindungsgemäßes Zweikomponentenmittel aus der Tube herausgedrückt wird, mit einer Oxidationsmittel- zubereitung vermischt wird, die resultierenden Anwendungszubereitung auf die Fasern aufgebracht wird und nach einer Einwirkungszeit wieder abgespült wird.A second object of the present invention is a process for dyeing keratin fibers, in particular human hair, wherein a two-component agent according to the invention is pressed out of the tube, mixed with an oxidizing agent preparation, the resulting application preparation is applied to the fibers and again after an exposure time is rinsed off.
Die nachfolgenden Beispiele sollen den Gegenstand der vorliegenden Erfindung erläutern ohne ihn in irgendeiner Weise zu beschränken. AusführunqsbeispieleThe following examples are intended to explain the subject matter of the present invention without restricting it in any way. EXEMPLARY EMBODIMENTS
Es wurden die folgenden Rezepturen hergestellt. Die Mengenangaben verstehen sich soweit nichts anderes vermerkt ist - in Gewichtsprozent.The following recipes were made. Unless otherwise stated, the amounts stated are in percent by weight.
Rezepturen der Zubereitung (A)Formulations of the preparation (A)
Figure imgf000066_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000067_0001
In den Färbecremes A bis I wurden die folgenden Farbpulvermischungen a, b und c eingesetzt:The following color powder mixtures a, b and c were used in the coloring creams A to I:
Figure imgf000067_0002
Figure imgf000068_0001
Figure imgf000067_0002
Figure imgf000068_0001
Figure imgf000068_0002
Figure imgf000068_0002
Rezepturen der Zubereitungen (B)Formulations (B)
Figure imgf000069_0001
Figure imgf000069_0001
Figure imgf000069_0002
Figure imgf000070_0001
Figure imgf000071_0001
Ausfärbung Die Färbecremes A bis I wurden jeweils im Verhältnis 3:1 mit den Pflegekomponenten B1 und B2 beziehungsweise im Verhältnis 1 :1 mit den Pflegekomponenten B3 und B4 in einer Zweikammertube konfektioniert. Unmittelbar vor der Anwendung wurde das Zweikomponentenmittel aus der Zweikammertube in eine Apiikationsschale gegeben und dort mit der o.g. Oxidationsmittelzubereitung vermischt. Anschließend wurde die resultierende Anwendungszubereitung auf Humanhaar (Kerling Naturweiß) aufgebracht, dort einmassiert, bei Raumtemperatur für 30 min einwirken gelassen und anschließend ausgespült. Nach Trocknung der Haare wurden intensive Blond- , Rot- bzw. Blauschwarz- Nuancen erzielt.
Figure imgf000069_0002
Figure imgf000070_0001
Figure imgf000071_0001
Coloring The coloring creams A to I were each made up in a 3: 1 ratio with the care components B1 and B2 or in a 1: 1 ratio with the care components B3 and B4 in a two-chamber tube. Immediately before use, the two-component agent was placed in a two-chamber tube in an application bowl and mixed there with the above-mentioned oxidizing agent preparation. The resulting application preparation was then applied to human hair (Kerling natural white), massaged in there, left to act at room temperature for 30 min and then rinsed out. After drying the hair, intense shades of blonde, red or blue-black were achieved.
Verzeichnis der eingesetzten Handelsprodukte Die im Rahmen der Beispiele eingesetzten Handelsprodukte sind wie folgt definiert:List of commercial products used The commercial products used in the examples are defined as follows:
Acrysol® 22 Acrylpolymer (ca. 29.5 - 30.5% Festkörper in Wasser; INCI- Bezeichnung: Acrylates/Steareth-20 Methacrylate Copolymer) Akypo Soft 45 NV® Laurylalkohol-4.5-EO-Essigsäure-Natrium-Salz (mind. 21% Aktivsubstanzgehalt; INCI-Bezeichnung: Sodium Laureth-6 Carboxylate) (Chem-Y) Dehyquart® A-CA Trimethylhexadecylammoniumchlorid (ca. 24 -26 % Aktivsubstanz; INCI-Bezeichnung: Aqua (Water), Cetrimonium Chloride) (Cognis) Dehyton® K N,N-Dimethyl-N-(C8-18-kokosamidopropyl)ammoniumaceto- betain (ca. 30% Aktivsubstanz; INCI-Bezeichnung: Aqua (Water), Cocamidopropyl Betaine) (Cognis)Acrysol ® 22 acrylic polymer (approx. 29.5 - 30.5% solids in water; INCI name: Acrylates / Steareth-20 methacrylate copolymer) Akypo Soft 45 NV ® Lauryl alcohol-4.5-EO-acetic acid sodium salt (at least 21% active substance content; INCI name: Sodium Laureth-6 Carboxylate) (Chem-Y) Dehyquart ® A-CA trimethylhexadecylammonium chloride (approx. 24 -26% active substance; INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis) Dehyton ® KN, N-Dimethyl-N- (C8-18-kokosamidopropyl) ammonium acetobetaine (approx. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)
Edenor® C14 Myristinsäure (INCI-Bezeichnung: MYRISTIC ACID) (Cognis) Eumulgin® B 1 Cetylstearylalkohol mit ca. 12-EO-Einheiten (INCI- Bezeichnung: Ceteareth-12) (Cognis Eumulgin® B2 Cetylstearylalkohol mit ca. 20 EO-Einheiten (INCI- Bezeichnung: Ceteareth-20) (Cognis) Eutanol® G 2-Octyldodecylalkohol (INCI-Bezeichnung: Octyldodecanol) (Cognis) Hydrenol® D C16-18-Fettalkohol (INCI-Bezeichnung: Cetearyl alcohol) (Cognis) Kokoslorol® C12-18-Fettalkohol (INCI-Bezeichnung: Coconut Alcohol) (Cognis) Lamesoft® P065 Alkylpolyglucosid Ölsäuremonoglycerid Gemisch (ca. 65- 70%o Festkörper; INCI-Bezeichnung: Coco-Glucoside, Glyceryl Oleate, Aqua (Water)) (Cognis)Edenor ® C14 myristic acid (INCI name: MYRISTIC ACID) (Cognis) Eumulgin ® B 1 cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis Eumulgin ® B2 cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis) Eutanol ® G 2-octyldodecyl alcohol (INCI name: Octyldodecanol) (Cognis) Hydrenol ® D C16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis) Kokoslorol ® C12 -18-fatty alcohol (INCI name: Coconut Alcohol) (Cognis) Lamesoft ® P065 alkyl polyglucoside oleic acid monoglyceride mixture (approx. 65-70% o solids; INCI name: Coco-Glucoside, Glyceryl Oleate, Aqua (Water)) (Cognis)
Merquat® 100 Poly(dimethyldiallylammoniumchlorid) (ca. 40% Festkörper; INCI-Bezeichnung: Polyquaternium-6) (Ondeo Nalco) Mirapol® A 15 Poly[N-(3-(dimethylammonium)propyl]-N'-[3- ethylenoxyethylendimethyl-ammonium)-propyl]-hamstoff-di- chlorid (ca. 64% Festkörper in Wasser; INCI-Bezeichnung: Polyquaternium-2) (Rhodia)Merquat ® 100 poly (dimethyldiallylammonium chloride) (approx. 40% solids; INCI name: Polyquaternium-6) (Ondeo Nalco) Mirapol ® A 15 poly [N- (3- (dimethylammonium) propyl] -N '- [3-ethyleneoxyethylene dimethyl -ammonium) -propyl] -urea-di-chloride (approx. 64% solids in water; INCI name: Polyquaternium-2) (Rhodia)
Phopholipid® EFA (INCI-Bezeichnung:Linoleamidopropyl PG-Dimonium Chloride Phosphate) (Uniqema)Phopholipid ® EFA (INCI name: Linoleamidopropyl PG-Dimonium Chloride Phosphate) (Uniqema)
Plantacare® 12O0 UP C12-16-Fettalkohol-1.4-glucosid (ca. 50-53% Aktivsubstanzgehalt; INCI-Bezeichnung: Lauryl Glucoside, Aqua (Water)) (Cognis)Plantacare ® 12O0 UP C12-16-fatty alcohol-1.4-glucoside (approx. 50-53% active substance content; INCI name: Lauryl Glucoside, Aqua (Water)) (Cognis)
Polymer® W 37194 ca. 20Gew.-% Aktivsubstanzgehalt in Wasser; INCI- Bezeichnung: Acrylamidopropyltrimonium Chloride/Acrylates Copolymer (Stockhausen) Prisorine® 3501 Isooctadecansäure (INCI-Bezeichnung: Isostearic Acid) (Uniqema)Polymer ® W 37194 approx. 20% by weight active substance content in water; INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer (Stockhausen) Prisorine ® 3501 isooctadecanoic acid (INCI name: Isostearic Acid) (Uniqema)
Promois Silk® 1000 Collagen Hydrolysat (ca. 5-8% Festkörper; INCI- Bezeichnung: HYDROLYZED SILK) (Interorgana)Promois Silk ® 1000 collagen hydrolyzate (approx. 5-8% solids; INCI name: HYDROLYZED SILK) (Interorgana)
Texapon® K 14 S 70 C Laurylmyristylethersulfat-Natrium-Salz (ca. 68% bis 73% Aktivsubstanzgehalt'; INCI-Bezeichnung: Sodium Myreth Sulfate) (Cognis)Texapon ® K 14 S 70 C lauryl myristyl ether sulfate sodium salt (approx. 68% to 73% active substance content '; INCI name: Sodium Myreth Sulfate) (Cognis)
Texapon® N28 Laurylethersulfat-Natrium-Salz (mind. 26,5 % Aktivsubstanzgehalt; INCI-Bezeichnung: Sodium Laureth Sulfate) (Cognis)Texapon ® N28 lauryl ether sulfate sodium salt (at least 26.5% active substance content; INCI name: Sodium Laureth Sulfate) (Cognis)
Texapon® NSO Laurylethersulfat, Natriumsalz (ca. 27,5% Aktivsubstanz; INCI-Bezeichnung: Sodium Laureth Sulfate) (Cognis) Turpinal® SL 1-Hydroxyethan-1 ,1-diphosphonsäure (ca. 58 - 61% Aktivsubstanzgehalt; INCI-Bezeichnung: Etidronic Acid, Aqua (Water)) (Solutia) Texapon ® NSO lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (Cognis) Turpinal ® SL 1-hydroxyethane-1, 1-diphosphonic acid (approx. 58 - 61% active substance content; INCI name : Etidronic Acid, Aqua (Water)) (Solutia)

Claims

Patentansprüche claims
1. Zweikomponentenmittel zur Färbung keratinischer Fasern, umfassend eine erste Zubereitung (A), enthaltend mindestens ein Oxidationsfarbstoffvorprodukt, und eine zweite Zubereitung (B), enthaltend mindestens einen Pflegestoff, dadurch gekennzeichnet, dass die beiden Zubereitungen getrennt voneinander in den Kammern einer Zweikammertube konfektioniert sind.1. Two-component agent for dyeing keratin fibers, comprising a first preparation (A) containing at least one oxidation dye precursor, and a second preparation (B) containing at least one care substance, characterized in that the two preparations are packaged separately from one another in the chambers of a two-chamber tube ,
2. Zweikomponentenmittel nach Anspruch 1, dadurch gekennzeichnet, dass die Zubereitung (A) mindestens eine Entwicklerkomponente enthält.2. Two-component agent according to claim 1, characterized in that the preparation (A) contains at least one developer component.
3. Zweikomponentenmittel nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die Zubereitung (A) mindestens eine Kupplerkomponente enthält.3. Two-component agent according to one of claims 1 or 2, characterized in that the preparation (A) contains at least one coupler component.
4. Zweikomponentenmittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Zubereitung (A) weiterhin mindestens eine Vorstufe eines naturanalogen Farbstoffs enthält.4. Two-component agent according to one of claims 1 to 3, characterized in that the preparation (A) further contains at least one precursor of a nature-analog dye.
5. Zweikomponentenmittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Zubereitung (A) weiterhin mindestens einen direktziehenden Farbstoff enthält.5. Two-component agent according to one of claims 1 to 4, characterized in that the preparation (A) further contains at least one substantive dye.
6. Zweikomponentenmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Zubereitung (B) mindestens ein kationisches Tensid enthält.6. Two-component agent according to one of claims 1 to 5, characterized in that the preparation (B) contains at least one cationic surfactant.
7. Zweikomponentenmittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Zubereitung (B) mindestens ein pflegendes Polymer enthält.7. Two-component agent according to one of claims 1 to 6, characterized in that the preparation (B) contains at least one nourishing polymer.
8. Zweikomponentenmittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Zubereitung (B) mindestens einen UV-Filter enthält.8. Two-component agent according to one of claims 1 to 7, characterized in that the preparation (B) contains at least one UV filter.
9. Zweikomponentenmittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Zubereitung (B) mindestens ein Vitamin, ein Provitamin, eine Vitarninvorstufe und/oder eines derer Derivate enthält.9. Two-component agent according to one of claims 1 to 8, characterized in that the preparation (B) contains at least one vitamin, a provitamin, a vitamin precursor and / or one of their derivatives.
10. Zweikomponentenmittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Zubereitung (B) mindestens einen Pflanzenextrakt enthält. 10. Two-component agent according to one of claims 1 to 9, characterized in that the preparation (B) contains at least one plant extract.
11. Zweikomponentenmittel nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Zubereitung (B) mindestens ein Proteinhydrolysat und/oder eines seiner Derivate enthält.11. Two-component agent according to one of claims 1 to 10, characterized in that the preparation (B) contains at least one protein hydrolyzate and / or one of its derivatives.
12. Zweikomponentenmittel nach einem der Ansprüche 1 bis 11 , dadurch gekennzeichnet, dass die Zubereitung (B) mindestens eine Verbindung, ausgewählt aus Ectoin oder Ectoinderivaten, Allantoin, Taurin und Bisabolol, enthält.12. Two-component agent according to one of claims 1 to 11, characterized in that the preparation (B) contains at least one compound selected from ectoin or ectoin derivatives, allantoin, taurine and bisabolol.
13. Zweikomponentemittel nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Zubereitung (B) mindestens ein Mono- bzw. Oligosaccharid enthält.13. Two-component agent according to one of claims 1 to 12, characterized in that the preparation (B) contains at least one mono- or oligosaccharide.
14. Zweikomponentenmittel nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass die Zubereitung (B) mindestens ein Silikonöl und/oder ein Silikongum enthält.14. Two-component agent according to one of claims 1 to 13, characterized in that the preparation (B) contains at least one silicone oil and / or a silicone gum.
15. Zweikomponentenmittel nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass die Zubereitung (B) mindestens einen Ölkörper enthält.15. Two-component agent according to one of claims 1 to 14, characterized in that the preparation (B) contains at least one oil body.
16. Zweikammertube, enthaltend in einer ersten Kammer eine Zubereitung (A), enthaltend mindestens ein Oxidationsfarbstoffvorprodukt, und in einer zweiten Kammer eine Zubereitung (B), enthaltend mindestens einen Pflegestoff.16. Two-chamber tube containing a preparation (A) containing at least one oxidation dye precursor in a first chamber and a preparation (B) containing at least one care substance in a second chamber.
17. Zweikammertube nach Anspruch 16, dadurch gekennzeichnet, dass die Zubereitungen in einem Verhältnis von (A):(B) entsprechend 1:1 bis 1:3 aus der Tube austreten.17. Two-chamber tube according to claim 16, characterized in that the preparations emerge from the tube in a ratio of (A) :( B) corresponding to 1: 1 to 1: 3.
18. Zweikammertube nach einem der Ansprüche 16 oder 17, dadurch gekennzeichnet, dass die eine Zubereitung als Streifen in dem aus der anderen Komponenten gebildeten Austrittsstrang enthalten ist.18. Two-chamber tube according to one of claims 16 or 17, characterized in that the one preparation is contained as a strip in the outlet strand formed from the other components.
19. Verfahren zur Färbung von keratinischen Fasern, insbesondere menschlichen Haaren, dadurch gekennzeichnet, dass ein Zweikomponentenmittel nach einem der Ansprüche 1 bis 18 aus der Tube herausgedrückt wird, mit einer Oxidationsmittelzubereitung vermischt wird, die resultierende Anwendungszubereitung auf die Fasern aufgebracht wird und nach einer Einwirkungszeit wieder abgespült wird. 19. A process for dyeing keratin fibers, in particular human hair, characterized in that a two-component agent according to one of claims 1 to 18 is pressed out of the tube, mixed with an oxidizing agent preparation, the resulting application preparation is applied to the fibers and after an exposure time is rinsed off again.
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US7294153B2 (en) 2007-11-13
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